Recent Advances in Asymmetric Synthesis of Р-Stereogenic Phosphorus Compounds

  • Oleg I. KolodiazhnyiEmail author
Part of the Topics in Current Chemistry book series (TOPCURRCHEM, volume 360)


This chapter points out significant advances in the asymmetric synthesis of P-chiral organophosphorus compounds with many applications in stereoselective synthesis and in asymmetric catalysis, making reference to updated literature findings as well as the author’s original research. Asymmetric addition and cycloaddition reactions, oxidation, including metal catalyzed and non-metal biocatalytic methods are described, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Use of chiral organophosphorus compounds in some asymmetric transformations such as hydrogenation and alkyl/arylation reactions is also discussed.


Asymmetric catalysis Asymmetric synthesis Biocatalysis Ephedrine P-Chiral phosphorus compounds Sparteine 








Amano AH

Pseudomonas cepacia lipase

Amano AK

Pseudomonas fluorescens lipase

Amano PS

Burkholderia cepacia lipase








Candida antarctica lipase (Chirazyme®L-2, Novozym 435b)






Candida rugosa lipase






Dibenzoyltartaric acid




Diastereoisomeric excess


Diisopropyl azodicarboxylate


















Diastereoisomeric ratio


Ethyl-(N′,N′-dimethylamino)propylcarbodiimide hydrochloride


Enantiomeric excess


Enantiomeric ratio








Lithium P,P′-di-tert-butylbiphenylide


Lipoprotein lipase






Mesyl (Methanesulfol)




Pseudomonas fluorescens lipase




Pig (porcine) liver esterase


Porcine pancreatic lipase




p-Toluenesulfonic acid




Room temperature


tert-Butylmethyl ether








Water soluble carbodiimide (EDC)




  1. 1.
    Darcel C, Uziel J, Jugé S (2008) In: Börner A (ed) Phosphorus ligands in asymmetric catalysis, vol 3. Wiley-VCH, Weinheim, pp 1211–1233Google Scholar
  2. 2.
    Erre G, Enthaler S, Junge K, Gladiali S, Beller M (2008) Synthesis and application of chiral monodentate phosphines in asymmetric hydrogenation. Coord Chem Rev 252:471–491Google Scholar
  3. 3.
    Harvey JS, Gouverneur V (2010) Catalytic enantioselective synthesis of P-stereogenic compounds. J Chem Soc Chem Commun 46:7477–7485Google Scholar
  4. 4.
    Grabulosa (ed) (2011) P-Stereogenic ligands in enantioselective catalysis. Royal Society of Chemistry, Cambridge, 501 ppGoogle Scholar
  5. 5.
    Bayardon J, Juge S (2012) P-Chiral ligands. In: Kamer PCJ, van Leeuwen PWNM (eds) Phosphorus(III) ligands in homogeneous catalysis: design and synthesis. Wiley, Hoboken, pp 355–389Google Scholar
  6. 6.
    Kolodiazhnyi OI (2012) Recent developments in the asymmetric synthesis of P-chiral phosphorus compounds. Tetrahedron Asymmetry 23:1–46Google Scholar
  7. 7.
    Grabulosa A, Granell J, Muller G (2007) Preparation of optically pure P-stereogenic trivalent phosphorus compounds. Coord Chem Rev 251:25–90Google Scholar
  8. 8.
    Kolodiazhnyi OI (2005) Asymmetric synthesis of hydroxyphosphonates. Tetrahedron Asymmetry 16:3295–3341Google Scholar
  9. 9.
    Wolf C (2008) Dynamic stereochemistry of chiral compounds: principles and applications. RSC, Cambridge, 512 ppGoogle Scholar
  10. 10.
    Guerrero Rios I, Rosas-Hernandez A, Martin E (2011) Recent advances in the application of chiral phosphine ligands in Pd-catalysed asymmetric allylic alkylation. Molecules 16:970–1010Google Scholar
  11. 11.
    Nemoto T (2008) Transition metal-catalyzed asymmetric reactions using P-chirogenic diaminophosphine oxides: DIAPHOXs. Chem Pharm Bull 56:1213–1228Google Scholar
  12. 12.
    Gatineau D, Giordano L, Buono G (2011) Bulky, optically active P-stereogenic phosphineboranes from pure H-menthylphosphinates. J Am Chem Soc 133:10728–10731Google Scholar
  13. 13.
    Moraleda D, Gatineau D, Martin D, Giordano L, Buono G (2008) A simple route to chiral phosphinous acid–boranes. J Chem Soc Chem Commun 3031–3033Google Scholar
  14. 14.
    Hoge G (2004) Stereoselective cyclization and pyramidal inversion strategies for P-chirogenic phospholane synthesis. J Am Chem Soc 126:9920–9921Google Scholar
  15. 15.
    Kolodiazhnyi OI (1998) Asymmetric synthesis of organophosphorus compounds. Tetrahedron Asymmetry 9:1279–1332Google Scholar
  16. 16.
    Humbel S, Bertrand C, Darcel C, Bauduin C, Jugé S (2003) Configurational stability of chlorophosphines. Inorg Chem 42:420–427Google Scholar
  17. 17.
    Hayakawa Y, Hyodo M, Kimura K, Kataoka M (2003) The first asymmetric synthesis of trialkyl phosphates on the basis of dynamic kinetic resolution in the phosphite method using a chiral source in a catalytic manner. J Chem Soc Chem Commun pp 1704–1705Google Scholar
  18. 18.
    Reichl KD, Ess DH, Radosevich AT (2013) Catalyzing pyramidal inversion: configurational lability of P-stereogenic phosphines via single electron oxidation. J Am Chem Soc 135:9354–9357Google Scholar
  19. 19.
    Imamoto T, Tamura K, Ogura T, Ikematsu Y, Mayama D, Sugiya M (2010) Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes. Tetrahedron Asymmetry 21:1522–1528Google Scholar
  20. 20.
    Montchamp J-L (2013) Organophosphorus synthesis without phosphorus trichloride: the case for the hypophosphorous pathway. Phosphorus Sulfur Silicon 188:66–75Google Scholar
  21. 21.
    Cain MF, Glueck DS, Golen JA, Rheingold AL (2012) Asymmetric synthesis and metal complexes of a С3-symmetric P-stereogenic triphosphine, (R)-MeSi(CH2PMe(t-Bu))3 (MT-Siliphos). Organometallics 31:775–778Google Scholar
  22. 22.
    Korpiun O, Lewis RA, Chickos J, Mislow K (1968) Synthesis and absolute configuration of optically active phosphine oxides and phosphinates. J Am Chem Soc 90:4842–4846Google Scholar
  23. 23.
    Crépy KVL, Imamoto TP (2003) Chirogenic phosphine ligands In: Majoral J-P (ed) Topics in Current Chemistry, vol 229. Springer-Verlag, Berlin, Heidelberg, pp 1–41Google Scholar
  24. 24.
    Xu Q, Zhao C-Q, Han L-B (2008) Stereospecific nucleophilic substitution of optically pure H-phosphinates: a general way for the preparation of chiral P-stereogenic phosphine oxides. J Am Chem Soc 130:12648Google Scholar
  25. 25.
    Leyris A, Bigeault J, Nuel D, Giordano L, Buono G (2007) Enantioselective synthesis of secondary phosphine oxides from (R P)-(−)-menthyl hydrogenophenylphosphinate. Tetrahedron Lett 48:5247–5250Google Scholar
  26. 26.
    Kolodiazhnyi OI (2005) (1R,2S,5R)-Menthyl phosphinate and its properties. J Russ Gen Chem 75:656–657Google Scholar
  27. 27.
    Kolodiazhna AO (2009) Asymmetric synthesis of hydroxyphosphonates and their derivatives with potential bioilogical activity. PhD Thesis IBONCH, Kiev, 150 pp
  28. 28.
    Fisher HC, Prost L, Montchamp J-L (2013) Organophosphorus chemistry without PCl3: a bridge from hypophosphorous acid to H-phosphonate diesters. Eur J Org Chem 7973–7978Google Scholar
  29. 29.
    Bravo-Altamirano K, Coudray L, Deal EL, Montchamp J-L (2010) Strategies for the asymmetric synthesis of H-phosphinate esters. Org Biomol Chem 8:5541–5551Google Scholar
  30. 30.
    Berger O, Montchamp J-L (2013) A general strategy for the synthesis of P-stereogenic compounds. Angew Chem Int Ed 52:11377–11380Google Scholar
  31. 31.
    Coudray L, Montchamp J-L (2008) Green, palladium-catalyzed synthesis of benzylic H-phosphinates from hypophosphorous acid and benzylic alcohols. Eur J Org Chem 4101–4103Google Scholar
  32. 32.
    Cardellicchio C, Naso F, Annunziata M, Capozzi M (2004) A convenient route to the phosphorus and sulfur stereoisomers of ethyl menthyl (methylsulfinyl)methylphosphonate. Tetrahedron Asymmetry 15:1471–1476Google Scholar
  33. 33.
    Kolodiazhnyi OI, Sheiko S, Grishkun EV (2000) C3-Symmetric trialkyl phosphites as starting compounds of asymmetric synthesis. Heteroatom Chem 11:138–143Google Scholar
  34. 34.
    Oliana M, King F, Horton PN, Hursthouse MB, Hii KK (2006) Practical synthesis of chiral vinylphosphine oxides by direct nucleophilic substitution. Stereodivergent synthesis of aminophosphine ligands. J Org Chem 71:2472–2479Google Scholar
  35. 35.
    Cristau H-J, Monbrun J, Schleiss J, Virieux D, Pirat J-L (2005) First synthesis of P-aryl-phosphinosugars, organophosphorus analogues of C-arylglycosides. Tetrahedron Lett 46:3741–3744Google Scholar
  36. 36.
    Ferry A, Malik G, Retailleau P, Guinchard X, Crich D (2013) Alternative synthesis of P-chiral phosphonite-borane complexes: application to the synthesis of phostone − phostone dimers. J Org Chem 78:6858–6867Google Scholar
  37. 37.
    Kolodiazhnyi OI, Gryshkun EV, Andrushko NV, Freytag M, Jones PG, Schmutzler R (2003) Asymmetric synthesis of chiral N-(1-methylbenzyl)aminophosphines. Tetrahedron Asymmetry 14:181–183Google Scholar
  38. 38.
    Gryshkun EV, Andrushko NV, Kolodiazhnyi OI (2004) Stereoselective reactions of chiral amines with racemic chlorophosphines. Phosphorus Sulfur Silicon 179:1027–1046Google Scholar
  39. 39.
    Kolodiazhnyi OI, Andrushko NV, Gryshkun ЕВ (2004) Stereoselective reactions of optically active derivatives of α-methylbenzylaminophosphine. J Russ Gen Chem 74:515–522Google Scholar
  40. 40.
    Gryshkun ЕV, Kolodiazhna AO, Kolodiazhnyi OI (2003) Synthesis of chiral tert-butylphenylphosphine oxide. J Russ Gen Chem 73:1823–1824Google Scholar
  41. 41.
    Reves M, Ferrer C, Leon T, Doran S, Etayo P, Vidal-Ferran A, Riera A, Verdaguer X (2010) Primary and secondary aminophosphines as novel P-stereogenic building blocks for ligand synthesis. Angew Chem Int Ed 49:9452–9455Google Scholar
  42. 42.
    Len T, Parera M, Roglans A, Riera A, Verdaguer X (2012) Chiral N-phosphino sulfinamide ligands in rhodium(I)-catalyzed [2+2+2]-cycloaddition reactions. Angew Chem Int Ed 51:6951–6955Google Scholar
  43. 43.
    Grabulosa A, Doran S, Brandariz G, Muller G, Benet-Buchholz J, Riera A, Verdaguer X (2014) Nickel(II) and palladium(II) complexes of the small-bite-angle P-stereogenic diphosphine ligand MaxPHOS and its monosulfide. Organometallics 33:692–701Google Scholar
  44. 44.
    Brun S, Parera M, Pla-Quintana A, Roglans A, León T, Achard T, Solà J, Verdaguer X, Riera A (2010) P-Stereogenic secondary iminophosphorane ligands and their rhodium(I) complexes: taking advantage of NH/PH tautomerism. Tetrahedron 66:9032–9040Google Scholar
  45. 45.
    Kimura T, Murai T (2005) Enantiomerically pure P-chiral phosphinoselenoic chlorides: inversion of configuration at the P-chirogenic center in the synthesis and reaction of these substances. J Chem Soc Chem Commun 4077–4079Google Scholar
  46. 46.
    Kimura T, Murai T (2004) P-Chiral phosphinoselenoic chlorides and optically active P-chiral phosphinoselenoic amides: synthesis and stereospecific interconversion with extrusion and addition reactions of the selenium atom. Chem Lett 33:878–879Google Scholar
  47. 47.
    Casimiro M, Roces L, Garcıa-Granda S, Iglesias MJ, Lopez Ortiz F (2013) Directed ortho-lithiation of aminophosphazenes: an efficient route to the stereoselective synthesis of P-chiral compounds. Org Lett 15:2378–2381Google Scholar
  48. 48.
    Adams H, Collins RC, Jones S, Warner CJA (2011) Enantioselective preparation of P-chiral phosphine oxides. Org Lett 13:6576–6579Google Scholar
  49. 49.
    Han ZS, Goyal N, Herbage MA, Sieber JD, Qu B, Xu Y, Li Z, Reeves JT, Desrosiers J-N, Ma S, Grinberg N, Lee H, Mangunuru HPR, Zhang Y, Krishnamurthy D, Lu BZ, Song JJ, Wang G, Senanayake CH (2013) Efficient asymmetric synthesis of P-chiral phosphine oxides via properly designed and activated benzoxazaphosphinine-2-oxide agents. J Am Chem Soc 135:2474–2477Google Scholar
  50. 50.
    Nemoto T, Hamada Y (2007) Pd-catalyzed asymmetric allylic substitution reactions using P-chirogenic diaminophosphine oxides: DIAPHOXs. Chem Record 7:150–158Google Scholar
  51. 51.
    Maienza F, Spindler F, Thommen M, Pugin B, Malan C, Mezzetti A (2002) Exploring stereogenic phosphorus: synthetic strategies for diphosphines containing bulky, highly symmetric substituents. J Org Chem 67:5239–5249Google Scholar
  52. 52.
    Jugé S (2008) Enantioselective synthesis of P-chirogenic phosphorus compounds via the ephedrine-borane complex methodology. Phosphorus Sulfur Silicon 183:233–248Google Scholar
  53. 53.
    Rippert J, Linden A, Hansen HJ (2000) Formation of diastereoisomerically pure oxazaphospholes and their reaction to chiral phosphane-borane adducts. Helv Chim Acta 83:311–321Google Scholar
  54. 54.
    Johansson JM, Kann N, Larsson K (2004) (2R,4S,5R)-3,4-Dimethyl-5-phenyl-2-[4-(trifluoromethyl)phenyl]-1,3,2-oxazaphospholidine(P-B)borane. Acta Cryst E60:o287–o288Google Scholar
  55. 55.
    Leon T, Riera A, Verdaguer X (2011) Stereoselective synthesis of P-stereogenic aminophosphines: ring opening of bulky oxazaphospholidines. J Am Chem Soc 133:5740–5743Google Scholar
  56. 56.
    Zijlstra H, León T, de Cózar A, Fonseca Guerra C, Byrom D, Riera A, Verdaguer X, Bickelhaupt FM (2013) Stereodivergent SN2@P reactions of borane oxazaphospholidines: experimental and theoretical studies. J Am Chem Soc 135:4483–4491Google Scholar
  57. 57.
    Khiri N, Bertrand E, Ondel-Eymin M-J, Rousselin Y, Bayardon J, Harvey PD, Juge S (2010) Enantioselective hydrogenation catalysis aided by a σ-bonded calix[4]arene to a P-chirogenic aminophosphane phosphinite rhodium complex. Organometallics 29:3622–3631Google Scholar
  58. 58.
    Imamoto T, Saitoh Y, Koide A, Ogura T, Yoshida K (2007) Synthesis and enantioselectivity of P-chiral phosphine ligands with alkynyl groups. Angew Chem Intern Ed 46:8636–8639Google Scholar
  59. 59.
    Salomon C, Dal Molin S, Fortin D, Mugnier Y, Boere RT, Juge S, Harvey PD (2010) The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster. J Chem Soc Dalton Trans 39:10068–10075Google Scholar
  60. 60.
    Bauduin C, Moulin D, Kaloun EB, Darcel C, Jugé S (2003) Highly enantiomerically enriched chlorophosphine boranes: synthesis and applications as P-chirogenic electrophilic blocks. J Org Chem 68:4293–4301Google Scholar
  61. 61.
    Darcel C, Moulin D, Henry JC, Lagrelette M, Richard P, Harvey PD, Jugé S (2007) Modular P-chirogenic aminophosphane-phosphinite ligands for Rh-catalyzed asymmetric hydrogenation: a new model for prediction of enantioselectivity. Eur J Org Chem 13:2078–2090Google Scholar
  62. 62.
    Colby EA, Jamison TF (2003) P-Chiral, monodentate ferrocenyl phosphines, novel ligands for asymmetric catalysis. J Org Chem 68:156–166Google Scholar
  63. 63.
    Imamoto T, Tamura K, Zhang Z, Horiuchi Y, Sugiya M, Yoshida K, Yanagisawa A, Gridnev ID (2012) Rigid P-chiral phosphine ligands with tert-butylmethylphosphino groups for rhodium-catalyzed asymmetric hydrogenation of functionalized alkenes. J Am Chem Soc 134:1754–1769Google Scholar
  64. 64.
    Vinci D, Mateus N, Wu X, Hancock F, Steiner A, Xiao J (2006) Oxazaphospholidine-oxide as an efficient ortho-directing group for the diastereoselective deprotonation of ferrocene. Org Lett 8:215–218Google Scholar
  65. 65.
    Grabulosa A, Muller G, Ordinas JI, Mezzetti A, Maestro MA, Font-Bardia M, Solans X (2005) Allylpalladium complexes with P-stereogenic monodentate phosphines. application in the asymmetric hydrovinylation of styrene. Organometallics 24:4961–4973Google Scholar
  66. 66.
    Lam H, Horton PN, Hursthouse MB, Aldous DJ, Hii KK (2005) Synthesis of P-chirogenic diarylphosphinoacetic acids and their proline derivatives for palladium-catalysed allylic alkylation reactions. Tetrahedron Lett 46:8145–8148Google Scholar
  67. 67.
    Leyris A, Nuel D, Giordano L, Achard M, Buono G (2005) Enantioselective synthesis of both enantiomers of tert-butylphenylphosphine oxide from (S)-prolinol. Tetrahedron Lett 46:8677–8680Google Scholar
  68. 68.
    Ngono CJ, Constantieux T, Buono G (2006) Diastereoselective synthesis of new P-stereogenic (ortho-hydroxyaryl)-diazaphospholidine–borane complexes by a totally stereoselective P–O to P–C migration rearrangement. Eur J Org Chem 1499–1507Google Scholar
  69. 69.
    Toselli N, Fortrie R, Martin D, Buono G (2010) New P-stereogenic triaminophosphines and their derivatives: synthesis, structure, conformational study, and application as chiral ligands. Tetrahedron Asymmetry 21:1238–1245Google Scholar
  70. 70.
    Delapierre G, Achard M, Buono G (2002) New P-stereogenic triaminophosphines and their derivatives: synthesis, structure, conformational study, and application as chiral ligands. Tetrahedron Lett 43:4025–4028Google Scholar
  71. 71.
    Rajendran KV, Gilheany DG (2012) Identification of a key intermediate in the asymmetric Appel process: one pot stereoselective synthesis of P-stereogenic phosphines and phosphine boranes from racemic phosphine oxides. J Chem Soc Chem Commun 48:10040–10042Google Scholar
  72. 72.
    Bergin E, O'Connor CT, Robinson SB, McGarrigle EM, O’Mahony CP, Gilheany DG (2007) Synthesis of P-stereogenic phosphorus compounds. Asymmetric oxidation of phosphines under Appel conditions. J Am Chem Soc 129:9566–9567Google Scholar
  73. 73.
    Rajendran KV, Kennedy L, Gilheany DG (2010) P-Stereogenic phosphorus compounds: effect of aryl substituents on the oxidation of arylmethylphenylphosphanes under asymmetric Appel conditions. Eur J Org Chem 5642–5649Google Scholar
  74. 74.
    Rajendran KV, Kudavalli JS, Dunne KS, Gilheany DG (2012) A U-turn in the asymmetric Appel reaction: stereospecific reduction of diastereomerically enriched alkoxyphosphonium salts allows the asymmetric synthesis of P-stereogenic phosphanes and phosphane boranes. Eur J Org Chem 2720–2723Google Scholar
  75. 75.
    Rajendran KV, Kennedy L, O’Connor CT, Bergin E, Gilheany DG (2013) Systematic survey of positive chlorine sources in the asymmetric Appel reaction: oxalyl chloride as a new phosphine activator. Tetrahedron Lett 54:7009–7012Google Scholar
  76. 76.
    Carr DJ, Kudavalli JS, Dunne KS, Müller-Bunz H, Gilheany DG (2013) Synthesis of 2,3-dihydro-1-phenylbenzo[b]phosphole (1-phenylphosphindane) and its use as a mechanistic test in the asymmetric Appel reaction: decisive evidence against involvement of pseudorotation in the stereoselecting step. J Org Chem 78:10500–10505Google Scholar
  77. 77.
    Nikitin K, Rajendran KV, Müller-Bunz H, Gilheany DG (2014) Turning regioselectivity into stereoselectivity: efficient dual resolution of P-stereogenic phosphine oxides through bifurcation of the reaction pathway of a common intermediate. Angew Chem Int Ed 53:1906–1909Google Scholar
  78. 78.
    Muci AR, Campos KR, Evans DA (1995) Enantioselective deprotonation as a vehicle for the asymmetric synthesis of C2-symmetric P-chiral diphosphines. J Am Chem Soc 117:9075–9076Google Scholar
  79. 79.
    Strohmann C, Strohfeldt K, Schildbach D, McGrath MJ, O'Brien P (2004) Crystal structures of (+)-sparteine surrogate adducts of methyllithium and phenyllithium. Organometallics 23:5389–5391Google Scholar
  80. 80.
    Strohmann C, Seibel T, Strohfeldt K (2003) Monomeric butyllithium compound [t-BuLi · (−)-sparteine]: molecular structure of the first monomeric butyllithium compound. Angew Chem Int Ed 42:4531–4533Google Scholar
  81. 81.
    Vestergren M, Eriksson J, Hilmersson G, Håkansson MJ (2003) Giving phenyllithium a right-handed double-helical twist. Syntheses and crystal structures of enantiopure alkyl-, aryl-, and amidolithium aggregates. J Organomet Chem 682:172–179Google Scholar
  82. 82.
    Genet C, Canipa SJ, O’Brien P, Taylor S (2006) Catalytic asymmetric synthesis of ferrocenes and P-stereogenic bisphosphines. J Am Chem Soc 128:9336–9337Google Scholar
  83. 83.
    Granander J, Secci F, Canipa SJ, O’Brien P, Kelly B (2011) One-ligand catalytic asymmetric deprotonation of a phosphine borane: synthesis of P-stereogenic bisphosphine ligands. J Org Chem 76:4794–4799Google Scholar
  84. 84.
    Imamoto T, Nishimura M, Koide A, Yoshida K (2007) t-Bu-QuinoxP* ligand: applications in asymmetric Pd-catalyzed allylic substitution and Ru-catalyzed hydrogenation. J Org Chem 72:7413–7416Google Scholar
  85. 85.
    Wu X, O’Brien P, Ellwood S, Secci F, Kelly B (2013) Synthesis of P-stereogenic phospholene boranes via asymmetric deprotonation and ring-closing metathesis. Org Lett 15:192–195Google Scholar
  86. 86.
    Gammon JJ, Canipa SJ, O’Brien P, Kelly B, Taylor S (2008) Catalytic asymmetric deprotonation of phosphine boranes and sulfides as a route to P-stereogenic compounds. J Chem Soc Chem Commun 3750–3752Google Scholar
  87. 87.
    Johansson MJ, Berglund S, Hu Y, Andersson KHO, Kann N (2012) Parallel and modular synthesis of P-chirogenic P,O-ligands. ACS Comb Sci 14:304–308Google Scholar
  88. 88.
    Dolhem F, Johansson MJ, Antonsson T, Kann N (2006) P-Chirogenic α-carboxyphosphine boranes as effective pre-ligands in palladium-catalyzed asymmetric reactions. Synlett 3389–3394Google Scholar
  89. 89.
    Johansson MJ, Schwartz L, Amedjkouh M, Kann N (2004) New chiral amine ligands in the desymmetrization of prochiral phosphine boranes. Tetrahedron Asymmetry 15:3531–3538Google Scholar
  90. 90.
    Morisaki Y, Imoto H, Tsurui K, Chujo Y (2009) Practical synthesis of P-stereogenic diphosphacrowns. Org Lett 11:2241–2244Google Scholar
  91. 91.
    Morisaki Y, Imoto H, Hirano K, Hayashi T, Chujo Y (2011) Synthesis of enantiomerically pure P-stereogenic diphosphacrowns and their palladium complexes. J Org Chem 76:1795–1803Google Scholar
  92. 92.
    Morisaki Y, Kato R, Chujo Y (2013) Synthesis of enantiopure P-stereogenic diphosphacrowns using P-stereogenic secondary phosphines. J Org Chem 78:2769–2774Google Scholar
  93. 93.
    Canipa SJ, O’Brien P, Taylor S (2009) Catalytic asymmetric deprotonation of a phosphine borane: comparison of two-ligand and one-ligand catalysis. Tetrahedron Asymmetry 20:2407–2412Google Scholar
  94. 94.
    Johansson MJ, Schwartz LO, Amedjkouh M, Kann NC (2004) Desymmetrization of prochiral phosphanes using derivatives of (−)-cytisine. Eur J Org Chem 1894–1896Google Scholar
  95. 95.
    Johansson MJ, Andersson KHO, Kann N (2008) Modular asymmetric synthesis of P-chirogenic-amino phosphine boranes. J Org Chem 73:4458–4463Google Scholar
  96. 96.
    Morisaki Y, Imoto H, Ouchi Y, Nagata Y, Chujo Y (2008) Stereospecific construction of a trans-1,4-diphosphacyclohexane skeleton. Org Lett 10:1489–1492Google Scholar
  97. 97.
    Imoto H, Morisaki Y, Chujo Y (2010) Synthesis and coordination behaviors of P-stereogenic polymers. J Chem Soc Chem Commun 46:7542–7544Google Scholar
  98. 98.
    Ouchi Y, Morisaki Y, Chujo Y (2006) Synthesis of photoresponsive polymers having P-chiral phosphine in the main chain. Polym Preprints 47:708–709Google Scholar
  99. 99.
    Ouchi Y, Morisaki Y, Ogoshi T, Chujo Y (2007) Synthesis of a stimuli-responsive P-chiral polymer with chiral phosphorus atoms and azobenzene moieties in the main chain. Chem Asian J 2:397–402Google Scholar
  100. 100.
    Oohara N, Katagiri K, Imamoto T (2003) A novel P-chirogenic phosphine ligand, (S, S)-1,2-bis-[(ferrocenyl)methylphosphino]ethane: synthesis and use in rhodium-catalyzed asymmetric hydrogenation and palladium-catalyzed asymmetric allylic alkylation. Tetrahedron Asymmetry 14:2171–2175Google Scholar
  101. 101.
    Hoge G (2003) Synthesis of both enantiomers of a P-chirogenic 1,2-bisphospholanoethane ligand via convergent routes and application to rhodium-catalyzed asymmetric hydrogenation of CI-1008 (Pregabalin). J Am Chem Soc 125:10219–10227Google Scholar
  102. 102.
    Tang W, Wang W, Zhang X (2003) Phospholane–oxazoline ligands for Ir-catalyzed asymmetric hydrogenation. Angew Chem Int Ed 42:943–946Google Scholar
  103. 103.
    Liu D, Zhang X (2005) Practical P-chiral phosphane ligand for Rh-catalyzed asymmetric hydrogenation. Eur J Org Chem 646–649Google Scholar
  104. 104.
    Tang W, Liu D, Zhang X (2003) Asymmetric hydrogenation of itaconic acid and enol acetate derivatives with the Rh-TangPhos catalyst. Org Lett 5:205–207Google Scholar
  105. 105.
    Gammon JJ, Gessner VH, Barker GR, Granander J, Whitwood AC, Strohmann C, O’Brien P, Kelly B (2010) Synthesis of P-stereogenic compounds via kinetic deprotonation and dynamic thermodynamic resolution of phosphine sulfides: opposite sense of induction using (−)-sparteine. J Am Chem Soc 132:13922–13927Google Scholar
  106. 106.
    Miyazaki T, Sugawara M, Danjo H, Imamoto T (2004) Dihydroboronium derivatives of (S, S)-1,2-bis(t-butylmethylphosphino)ethane as convenient chiral ligand precursors. Tetrahedron Lett 45:9341–9344Google Scholar
  107. 107.
    Imamoto T, Crepy KVL, Katagiri K (2004) Optically active 1,10-di-tert-butyl-2,20-dibenzophosphetenyl: a highly strained P-stereogenic diphosphine ligand. Tetrahedron Asymmetry 75:2213–2218Google Scholar
  108. 108.
    Gammon JJ, O’Brien P, Kelly B (2009) Regioselective lithiation of silyl phosphine sulfides: asymmetric synthesis of P-stereogenic compounds. Org Lett 11:5022–5025Google Scholar
  109. 109.
    Glueck DS (2008) Catalytic asymmetric synthesis of chiral phosphanes. Chem Eur J 14:7108–7117Google Scholar
  110. 110.
    Glueck DS (2008) Applications of 31P NMR spectroscopy in development of M(Duphos)-catalyzed asymmetric synthesis of P-stereogenic phosphines (M=Pt or Pd). Coord Chem Rev 252:2171–2179Google Scholar
  111. 111.
    Glueck DS (2007) Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines. Synlett 2627–2634Google Scholar
  112. 112.
    Moncarz JR, Brunker TJ, Jewett JC, Orchowski M, Glueck DS, Sommer RD, Lam K-C, Incarvito CD, Concolino TE, Ceccarelli C, Zakharov LN, Rheingold AL (2003) Palladium-catalyzed asymmetric phosphination. enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination. Organometallics 22:3205–3221Google Scholar
  113. 113.
    Glueck DS (2010) Recent advances in metal-catalyzed C–P bond formation. Topics Organomet Chem 31:65–100Google Scholar
  114. 114.
    Moncarz JR, Brunker TJ, Glueck DS, Sommer RD, Rheingold AL (2003) Stereochemistry of palladium-mediated synthesis of PAMP−BH3: retention of configuration at P in formation of Pd−P and P−C bonds. J Am Chem Soc 125:1180–1181Google Scholar
  115. 115.
    Brunker TJ, Anderson BJ, Blank NF, Glueck DS, Rheingold AL (2007) Enantioselective synthesis of P-stereogenic benzophospholanes via palladium-catalyzed intramolecular cyclization. Org Lett 9:1109–1112Google Scholar
  116. 116.
    Guino-o MA, Zureick AH, Blank NF, Anderson BJ, Chapp TW, Kim Y, Glueck DS, Rheingold AL (2012) Synthesis and structure of platinum bis(phospholane) complexes Pt(diphos*)(R)(X), catalyst precursors for asymmetric phosphine alkylation. Organometallics 31:6900–6910Google Scholar
  117. 117.
    Chapp TW, Glueck DS, Golen JA, Moore CE, Rheingold AL (2010) Platinum-catalyzed asymmetric alkylation of bis(isitylphosphino)ethane: stereoselectivity reversal in successive formation of two P–C bonds. Organometallics 29:378–388Google Scholar
  118. 118.
    Scriban C, Glueck DS, DiPasquale AG, Rheingold AL (2006) Chiral platinum duphos terminal phosphido complexes: synthesis, structure, phosphido transfer, and ligand behavior. Organometallics 25:5435–5448Google Scholar
  119. 119.
    Chapp TW, Schoenfeld AJ, Glueck DS (2010) Effects of linker length on the rate and selectivity of platinum-catalyzed asymmetric alkylation of the bis(isitylphosphino)alkanes IsHP(CH2)nPHIs (Is = 2,4,6-(i-Pr)3C6H2, n = 1–5). Organometallics 29:2465–2473Google Scholar
  120. 120.
    Scriban C, Glueck DS, Golen JA, Rheingold AL (2007) Platinum-catalyzed asymmetric alkylation of a secondary phosphine: mechanism and origin of enantioselectivity. Organometallics 26:1788–1800Google Scholar
  121. 121.
    Scriban C, Glueck DS (2006) Platinum-catalyzed asymmetric alkylation of secondary phosphines: enantioselective synthesis of P-stereogenic phosphines. J Am Chem Soc 128:2788–2789Google Scholar
  122. 122.
    Scriban C, Glueck DS, Golen JA, Rheingold AL (2007) Platinum-catalyzed asymmetric alkylation of a secondary phosphine: mechanism and origin of enantioselectivity. Organometallics 26:5124Google Scholar
  123. 123.
    Anderson BJ, Guino-o MA, Glueck DS, Golen JA, DiPasquale AG, Liable-Sands LM, Rheingold AL (2008) Platinum-catalyzed enantioselective tandem alkylation/arylation of primary phosphines. Asymmetric synthesis of P-stereogenic 1-phosphaacenaphthenes. Org Lett 10:4425–4428Google Scholar
  124. 124.
    Scriban C (2009) Catalytic asymmetric phosphorus-carbon bond formation with platinum-phosphido complexes. Ph.D. thesis, pp 1–464.
  125. 125.
    Scriban C, Kovacik I, Glueck DS (2005) A protic additive suppresses formation of byproducts in platinum-catalyzed hydrophosphination of activated olefins. Evidence for P-C and C-C bond formation by Michael addition. Organometallics 24:4871–4874Google Scholar
  126. 126.
    Anderson BJ, Glueck DS, DiPasquale AG, Rheingold AL (2008) Substrate and catalyst screening in platinum-catalyzed asymmetric alkylation of bis(secondary) phosphines. Synthesis of an enantiomerically pure C2-symmetric diphosphine. Organometallics 27:4992–5001Google Scholar
  127. 127.
    Scriban C, Glueck DS (2006) Asymmetric catalytic synthesis of P-stereogenic phosphines via a nucleophilic ruthenium phosphido complex. J Am Chem Soc 128:2786–2787Google Scholar
  128. 128.
    Chan VS, Chiu M, Bergman RG, Toste FD (2009) Development of ruthenium catalysts for the enantioselective synthesis of P-stereogenic phosphines via nucleophilic phosphido intermediates. J Am Chem Soc 131:6021–6032Google Scholar
  129. 129.
    Gschwend B (2009) P-Chiral phosphorus ligands: synthesis and application in asymmetric hydrogenation inaugural dissertation, Basel,
  130. 130.
    Blank NF, McBroom KC, Glueck DS, Kassel WS, Rheingold AL (2006) Chirality breeding via asymmetric phosphination. Palladium-catalyzed diastereoselective synthesis of a P-stereogenic phosphine. Organometallics 25:1742–1748Google Scholar
  131. 131.
    Moncarz JR, Laritcheva NF, Glueck DS (2002) Palladium-catalyzed asymmetric phosphination: enantioselective synthesis of a P-chirogenic phosphine. J Am Chem Soc 124:13356–13357Google Scholar
  132. 132.
    Blank NF, Moncarz JR, Brunker TJ, Scriban C, Anderson BJ, Amir O, Glueck DS, Zakharov LN, Golen JA, Incarvito CD, Rheingold AL (2007) Palladium-catalyzed asymmetric phosphination. Scope, mechanism, and origin of enantioselectivity. J Am Chem Soc 129:6847–6858Google Scholar
  133. 133.
    Chan VS, Bergman RG, Toste FD (2007) Pd-catalyzed dynamic kinetic enantioselective arylation of silylphosphines. J Am Chem Soc 129:15122–15123Google Scholar
  134. 134.
    Pican S, Gaumont A-C (2005) Palladium catalysed enantioselective phosphination reactions using secondary phosphine-boranes and aryl iodide. J Chem Soc Chem Commun 2393–2395Google Scholar
  135. 135.
    Scriban C, Glueck DS (2012) Method for enantioselective synthesis of phosphorus-stereogenic phosphines. US 8,193,392 B2
  136. 136.
    Zhou SJ, Huang Z (2013) Chiral phosphines for palladium-catalyzed asymmetric alpha-arylation of ester enolates to produce tertiary stereocenters in high enantioselectivity. WO/2013/028132
  137. 137.
    Korff C, Helmchen G (2004) Preparation of chiral triarylphosphines by Pd-catalysed asymmetric P–C cross-coupling. J Chem Soc Chem Commun 530–531Google Scholar
  138. 138.
    Join B, Mimeau D, Delacroix O, Gaumont A-C (2006) Pallado-catalysed hydrophosphination of alkynes: access to enantioenriched P-stereogenic vinyl phosphine–boranes. J Chem Soc Chem Commun 3249–3251Google Scholar
  139. 139.
    Lu J, Ye J, Duan W-L (2013) Palladium-catalyzed asymmetric addition of diarylphosphines to α, β-unsaturated sulfonic esters for the synthesis of chiral phosphine sulfonate compounds. Org Lett 15:5016–5019Google Scholar
  140. 140.
    Rosenberg L (2013) Mechanisms of metal-catalyzed hydrophosphination of alkenes and alkynes. ACS Catal 3:2845–2855Google Scholar
  141. 141.
    Lebel H, Morin S, Paquet V (2003) Alkylation of phosphine boranes by phase-transfer catalysis. Org Lett 5:2347–2349Google Scholar
  142. 142.
    Reynolds SC, Hughes RP, Glueck DS, Rheingold AL (2012) Synthesis, reactivity, and resolution of a C2 symmetric, P-stereogenic benzodiphosphetane, a building block for chiral bis(phosphines). Org Lett 14:4238–4241Google Scholar
  143. 143.
    Dai L-X, Hou X-L (eds) (2010) Chiral ferrocenes in asymmetric catalysis: synthesis and applications. Wiley-VCH, Hoboken, p 431Google Scholar
  144. 144.
    Colacot TJ (2003) A concise update on the applications of chiral ferrocenyl phosphines in homogeneous catalysis leading to organic synthesis. Chem Rev 103:3101–3118Google Scholar
  145. 145.
    Chen WP, Mbafor W, Roberts SM, Whittall J (2006) A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands. J Am Chem Soc 128:3922–3923Google Scholar
  146. 146.
    Boaz NW, Mackenzie EB, Debenham SD, Large SE, Ponasik JA (2005) Synthesis and application of phosphinoferrocenylaminophosphine ligands for asymmetric catalysis. J Org Chem 70:1872–1880Google Scholar
  147. 147.
    Gschwend B, Pugin B, Bertogg A, Pfaltz A (2009) P-Chiral ferrocenephospholanes: synthesis, reactivity, metal complex chemistry and application in the asymmetric hydrogenation of olefins. Chem Eur J 15:12993–13007Google Scholar
  148. 148.
    Chen WP, McCormack PJ, Mohammed K, Mbafor W, Roberts SM, Whittall J (2007) Stereoselective synthesis of ferrocene-based c2-symmetric diphosphine ligands: application to the highly enantioselective hydrogenation of α-substituted cinnamic acids. Angew Chem Int Ed 46:4141–4144Google Scholar
  149. 149.
    Chen WP, Roberts SM, Whittall J, Steiner A (2006) An efficient and highly stereoselective synthesis of new P-chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation. J Chem Soc Chem Commun 2916–2918Google Scholar
  150. 150.
    Chen W, Spindler F, Pugin B, Nettekoven U (2013) ChenPhos: highly modular P-stereogenic C1-symmetric diphosphine ligands for the efficient asymmetric hydrogenation of α-substituted cinnamic acids. Angew Chem Intern Ed 52:8652–8656Google Scholar
  151. 151.
    Bansal RK, Karaghiosoff K, Gupta N, Gandhi N, Kumawata SK (2005) Diastereo- and regioselectivity in Diels–Alder reaction of [1,4,2] diazaphospholo[4,5-a]pyridines. Tetrahedron 61:10521–10528Google Scholar
  152. 152.
    Leung PH (2004) Asymmetric synthesis and organometallic chemistry of functionalized phosphines containing stereogenic phosphorus centers. Acc Chem Res 37:169–177Google Scholar
  153. 153.
    Ng JK-P, Chen S, Li Y, Tan G-K, Koh L-L, Leung P-H (2007) Cyclopalladation of the prochiral (di-tert-butyl)(diphenylmethyl)phosphine: kinetic lability of the corresponding (+)-phosphapalladacyclic Pd–C bond and the reluctance of the phosphine to bind in a monodentate fashion. Inorg Chem 46:5100–5109Google Scholar
  154. 154.
    Chen S, Pullarkat SA, Li Y, Leung P-H (2011) Synthesis of homo- and hetero-bimetallic arsenic complexes by means of regioselective monoinsertion of alkynylarsane into the Pd–C bond of a palladacycle. Eur J Inorg Chem 3111–3121Google Scholar
  155. 155.
    Qin Y, Lang H, Vittal JJ, Tan G-K, Selvaratnam S, White AJP, Williams DJ, Leung P-H (2003) Asymmetric synthesis and coordination chemistry of bidentate P-stereogenic phosphines containing ester and thionoester functionalities. Organometallics 22:3944–3950Google Scholar
  156. 156.
    Bungabong ML, Tan KW, Li Y, Selvaratnam SV, Dongol KG, Leung P-H (2007) A novel asymmetric hydroarsination reaction promoted by a chiral organopalladium complex. Inorg Chem 46:4733–4736Google Scholar
  157. 157.
    Ma M, Pullarkat SA, Yuan M, Zhang N, Li Y, Leung P-H (2009) Metal effects on the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine oxide. Organometallics 28:4886–4889Google Scholar
  158. 158.
    Li Y, Selvaratnam S, Vittal JJ, Leung PH (2003) A rational approach to the design and synthesis of chiral organopalladium-amine complexes. Inorg Chem 42:3229–3236Google Scholar
  159. 159.
    Yeo W-C, Chen S, Tan G-K, Leung P-H (2007) Synthesis of P-chiral phosphines via chiral metal template promoted asymmetric furan Diels–Alder reaction. J Organomet Chem 692:2539–2547Google Scholar
  160. 160.
    Yeo W-C, Tang L, Yan B, Tee S-Y, Koh LL, Tan G-K, Leung P-H (2005) Chiral metal template induced asymmetric synthesis of a mixed phosphine-phosphine oxide ligand. Organometallics 24:5581–5585Google Scholar
  161. 161.
    Yuan M, Pullarkat SA, Li Y, Lee Z-Y, Leung P-H (2010) Novel synthesis of chiral 1,3-diphosphines via palladium template promoted hydrophosphination and functional group transformation reactions. Organometallics 29:3582–3588Google Scholar
  162. 162.
    Yuan M, Zhang NA, Pullarkat S, Li Y, Liu F, Pham P-T, Leung P-H (2010) Asymmetric synthesis of functionalized 1,3-diphosphines via chiral palladium complex promoted hydrophosphination of activated olefins. Inorg Chem 49:989–996Google Scholar
  163. 163.
    Yeo WC, Vittal JJ, Koh LL, Tan GK, Leung PH (2004) Chiral metal template promoted asymmetric pyrrole Diels–Alder reaction between N-(diphenylphosphino)pyrrole and diphenylvinylphosphine. Organometallics 23:3474–3482Google Scholar
  164. 164.
    Chen S, Pullarkat SA, Li Y, Leung P-H (2011) Asymmetric synthesis of P-stereogenic homo- and heterobimetallic complexes via selective monoinsertion of dialkynylphosphine into the Pd–C bond of a palladacycle. Organometallics 30:1530–1550Google Scholar
  165. 165.
    Leung PH, Siah SY, White AJP, Williams DJ (1998) Asymmetric syntheses, structures and reactions of palladium(II) complexes containing thiolato- and sulfinyl-substituted P chiral phosphines. J Chem Soc Dalton Trans 893–899Google Scholar
  166. 166.
    Chen K, Pullarkat SA, Li Y, Leung PH (2012) Chiral cyclopalladated complex promoted asymmetric synthesis of diester-substituted P, N-ligands via stepwise hydrophosphination and hydroamination reactions. J Chem Soc Dalton Trans 41:5391–5400Google Scholar
  167. 167.
    Chen S, Ng JK-P, Pullarkat SA, Liu F, Li Y, Leung P-H (2010) Asymmetric synthesis of new diphosphines and pyridylphosphines via a kinetic resolution process promoted and controlled by a chiral palladacycle. Organometallics 29:3374–3386Google Scholar
  168. 168.
    Huang Y, Li Y, Leung P-H, Hayashi T (2014) Asymmetric synthesis of P-stereogenic diarylphosphinites by palladium-catalyzed enantioselective addition of diarylphosphines to benzoquinones. J Am Chem Soc 136:4865–4868Google Scholar
  169. 169.
    Huang Y, Pullarkat SA, Teong S, Chew RJ, Li Y, Leung PH (2012) Palladacycle-catalyzed asymmetric intermolecular construction of chiral tertiary P-heterocycles by stepwise addition of H–P–H bonds to bis(enones). Organometallics 31:4871–4875Google Scholar
  170. 170.
    Möller T, Sárosi MB, Hey-Hawkins E (2012) Asymmetric phospha-Diels–Alder reaction: a stereoselective approach towards P-chiral phosphanes through diastereotopic face differentiation. Chem Eur J 18:16604–16607Google Scholar
  171. 171.
    Fukawa N, Osaka T, Noguchi K, Tanaka K (2010) Asymmetric synthesis and photophysical properties of benzopyrano- or naphthopyrano-fused helical phosphafluorenes. Org Lett 12:1324Google Scholar
  172. 172.
    Krasinski G, Cypryk M, Kwiatkowska M, Mikołajczyk M, Kiełbasinski P (2012) Molecular modeling of the lipase-catalyzed hydrolysis of acetoxymethyl(i-propoxy)phenylphosphine oxide and its P-borane analogue. J Mol Graph Model 38:290–297Google Scholar
  173. 173.
    Kiełbasinski P, Mikołajczyk M (2007) Chiral heteroatom-containing compounds. In: Matsuda T (ed) Future directions in biocatalysis. Elsevier, Amsterdam, pp 159–203Google Scholar
  174. 174.
    Shioji K, Kurauchi Y, Okuma K (2003) Novel synthesis of P-chiral hydroxymethylphosphine–boranes through lipase-catalyzed optical resolution. Bull Chem Soc Jpn 76:833–834Google Scholar
  175. 175.
    Kiełbasinski P, Albrycht M, Zurawinski R, Mikołajczyk M (2006) Lipase-mediated kinetic resolution of racemic and desymmetrization of prochiral organophosphorus P-boranes. J Mol Catal B 39:45–49Google Scholar
  176. 176.
    Kwiatkowska M, Krasiński G, Cypryk M, Cierpiał T, Kiełbasiński P (2011) Lipase-mediated stereoselective transformations of chiral organophosphorus P-boranes revisited: revision of the absolute configuration of alkoxy(hydroxymethyl)phenylphosphine P-boranes. Tetrahedron Asymmetry 22:1581–1590Google Scholar
  177. 177.
    Wiktelius D, Johansson MJ, Luthman K, Kann N (2005) A biocatalytic route to P-chirogenic compounds by lipase-catalyzed desymmetrization of a prochiral phosphine-borane. Org Lett 7:4991–4994Google Scholar
  178. 178.
    Kolodiazhnyi OI (2011) Enzymatic synthesis of organophosphorus compounds. Russ Chem Rev 80:883–910Google Scholar
  179. 179.
    Shioji K, Tashiro A, Shibata S, Okuma K (2003) Synthesis of bifunctional P-chiral hydroxy phosphinates; lipase-catalyzed stereoselective acylation of ethyl (1-hydroxyalkyl) phenylphosphinates. Tetrahedron Lett 44:1103–1105Google Scholar
  180. 180.
    Majewska P, Kafarski P, Lejczak B (2006) Simple and effective method for the deracemization of ethyl 1-hydroxyphosphinate using biocatalysts with lipolytic activity. Tetrahedron Asymmetry 17:2870–2875Google Scholar
  181. 181.
    Yamagishi T, Miyamae T, Yokomatsu T, Shibuya S (2004) Lipase-catalyzed kinetic resolution of α-hydroxy-H-phosphinates. Tetrahedron Lett 45:6713–6716Google Scholar
  182. 182.
    Yamagishi T, Mori J-I, Haruki T, Yokomatsu T (2011) A chemo-enzymatic synthesis of optically active 1,1-diethoxyethyl(aminomethyl)phosphinates: useful chiral building blocks for phosphinyl dipeptide isosteres. Tetrahedron Asymmetry 22:1358–1363Google Scholar
  183. 183.
    Albrycht M, Kiełbasinski P, Drabowicz J, Mikołajczyk M, Matsuda T, Harada T, Nakamura K (2005) Supercritical carbon dioxide as a reaction medium for enzymatic kinetic resolution of P-chiral hydroxymethanephosphinates. Tetrahedron Asymmetry 16:2015–2018Google Scholar
  184. 184.
    Shioji K, Ueyama T, Ueda N, Mutoh E, Kurisaki T, Wakita H, Okuma K (2008) Evaluation of enantioselectivity in lipase-catalyzed acylation of hydroxyalkylphosphine oxides. J Mol Cat B Enzym 55:146–151Google Scholar
  185. 185.
    Kiełbasinski P, Zurawinski R, Albrycht M, Mikołajczyk M (2003) The first enzymatic desymmetrizations of prochiral phosphine oxides. Tetrahedron Asymmetry 14:3379–3384Google Scholar
  186. 186.
    Li Y, Aubert SD, Maes EG, Raushel FM (2004) Enzymatic resolution of chiral phosphinate esters. J Am Chem Soc 126:8888–8889Google Scholar
  187. 187.
    Tsai P-C, Bigley A, Li Y, Ghanem E, Cadieux CL, Kasten SA, Reeves TE, Cerasoli DM, Raushel FM (2010) Stereoselective hydrolysis of organophosphate nerve agents by the bacterial phosphotriesterase. Biochemistry 49:7978–7987Google Scholar
  188. 188.
    Kim J, Tsai P-C, Chen S-L, Himo F, Almo SC, Raushel FM (2008) Structure of diethyl phosphate bound to the binuclear metal center of phosphotriesterase. Biochemistry 47:9497–9504Google Scholar
  189. 189.
    Li Y, Aubert SD, Raushel FM (2003) Operational control of stereoselectivity during the enzymatic hydrolysis of racemic organophosphorus compounds. J Am Chem Soc 125:7526–7527Google Scholar
  190. 190.
    Li WS, Li Y, Hill CM, Lum KT, Raushel FM (2002) Enzymatic synthesis of chiral organophosphothioates from prochiral precursors. J Am Chem Soc 124:3498–3499Google Scholar
  191. 191.
    Nowlan C, Li Y, Hermann JC, Evans T, Carpenter J, Ghanem E, Shoichet BK, Raushel FM (2006) Resolution of chiral phosphate phosphonate and phosphinate esters by an enantioselective enzyme library. J Am Chem Soc 128:15892–15902Google Scholar
  192. 192.
    Mikołajczyk M, Łuczak J, Kiełbasinski P, Colonna S (2009) Biocatalytic oxidation of thiophosphoryl compounds: a new chemo-enzymatic approach to enantiomeric insecticidal thionophosphates and their oxons. Tetrahedron Asymmetry 20:1948–1951Google Scholar
  193. 193.
    Kiełbasiński P, Rachwalski M, Kwiatkowska M, Mikołajczyk M, Wieczorek WM, Szyrej M, Sieroń L, Rutjes FPJT (2007) Enzyme-promoted desymmetrisation of prochiral bis(cyanomethyl)phenylphosphine oxide. Tetrahedron Asymmetry 18:2108–2112Google Scholar
  194. 194.
    Harvey JS, Malcolmson SJ, Dunne KS, Meek SJ, Thompson AL, Schrock RR, Hoveyda AH, Gouverneur V (2009) Enantioselective synthesis of P-stereogenic phosphinates and phosphine oxides by molybdenum-catalyzed asymmetric ring-closing metathesis. Angew Chem Int Ed Engl 48:762–766Google Scholar
  195. 195.
    Takizawa S, Rémond E, Arteaga FA, Yoshida Y, Sridharan V, Bayardon J, Jugé S, Sasai H (2013) P-Chirogenic organocatalysts: application to the aza-Morita–Baylis–Hillman (aza-MBH) reaction of ketimines. J Chem Soc Chem Commun 49:8392–8394Google Scholar
  196. 196.
    Francesco IN, Wagner A, Colobert F (2010) Stereoselective addition of Grignard reagents to new P-chirogenic N-phosphinoylimines. J Chem Soc Chem Commun 46:2139–2141Google Scholar
  197. 197.
    Francesco IN, Egloff C, Wagner A, Colobert F (2011) Stereoselective addition of Grignard reagents to new P-chirogenic N-phosphinoylbenzaldimines: effect of the phosphorus substituents on the stereoselectivity. Eur J Org Chem 4037–4045Google Scholar
  198. 198.
    Camus J-M, Andrieu J, Richard P, Poli R, Darcel C, Jugé S (2004) A P-chirogenic β-aminophosphine synthesis by diastereoselective reaction of the α-metallated PAMP–borane complex with benzaldimine. Tetrahedron Asymmetry 15:2061–2065Google Scholar
  199. 199.
    Busacca CA, Qu B, Farber E, Haddad N, Gret N, Saha AK, Eriksson MC, Wu J-P, Fandrick KR, Han S, Grinberg N, Ma S, Lee H, Li Z, Spinelli M, Gold A, Wang Z, Wang G, Wipf P, Senanayake CH (2013) [2,3]-Sigmatropic rearrangements of 2-phosphineborane 2-propen-1-ols: rapid access to enantioenriched diphosphine monoxide derivatives. Org Lett 15:1136–1139Google Scholar
  200. 200.
    Kaboudin B, Alaie S, Yokomatsu T (2011) Resolution of enantiomers of [α-hydroxy-(o-chlorophenyl)methyl]phosphinic acid via diastereomeric salt formation with enantiopure 1-phenylethylamines. Tetrahedron Asymmetry 22:1813–1816Google Scholar
  201. 201.
    Kaboudin B, Haruki T, Yamagishi T, Yokomatsu T (2007) Diastereoselective addition of α-substituted α-amino-H-phosphinates to imines using Yb(OTf)3 as an efficient Lewis acid catalyst. Tetrahedron 63:8199–8205Google Scholar
  202. 202.
    Ding B, Zhang Z, Xu Y, Liu Y, Sugiya M, Imamoto T, Zhang W (2013) P-Stereogenic PCP pincer–Pd complexes: synthesis and application in asymmetric addition of diarylphosphines to nitroalkenes. Org Lett 15:5476–5479Google Scholar
  203. 203.
    Huang K, Emge TJ, Zhang X (2014) Synthesis of a novel P-chiral 1,3-oxaphospholane from optically pure propylene oxide. Heteroatom Chem 25:131–134Google Scholar
  204. 204.
    Mohar B, Čusak A, Modec B, Stephan M (2013) P-Stereogenic phospholanes or phosphorinanes from o-biarylylphosphines: two bridges not too far. J Org Chem 78:4665–4673Google Scholar
  205. 205.
    Pereira MM, Calvete MJF, Carrilho RMB, Abreua AR (2013) Synthesis of binaphthyl based phosphine and phosphite ligands. Chem Soc Rev 42:6990–7027Google Scholar
  206. 206.
    Bagi P, Kállay M, Hessz D, Kubinyic M, Holczbauer T, Czugler M, Fogassy E, Keglevich G (2014) Resolution of 1-n-propoxy-3-methyl-3-phospholene 1-oxide by diastereomeric complex formation using TADDOL derivatives and calcium salts of O, O′-dibenzoyl-(2R,3R)- or O, O′-di-P-toluoyl-(2R,3R)-tartaric acid. Tetrahedron Asymmetry 25:318–326Google Scholar
  207. 207.
    Dziuba K, Flis A, Szmigielska A, Pietrusiewicz KM (2010) Efficient oxidative resolution of a P-stereogenic triarylphosphine and asymmetric synthesis of a P-stereogenic atropoisomeric biphenyl diphosphine dioxide. Tetrahedron Asymmetry 21:1401–1405Google Scholar
  208. 208.
    Holt J, Majc AM, Schudde EP, Pietrusiewicz KM, Sieroń L, Wieczorek W, Jerphagnon T, Arends IWCE, Hanefeld U, Minnaard AJ (2009) On the resolution of secondary phosphine oxides via diastereomeric complex formation: the case of tert-butylphenylphosphine oxide. Synthesis 2061–2065Google Scholar

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© Springer International Publishing Switzerland 2014

Authors and Affiliations

  1. 1.Institute of Bioorganic Chemistry and PetrochemistryNational Academy of Sciences of UkraineKievUkraine

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