Reagent-Controlled Lithiation–Borylation

Part of the Topics in Organometallic Chemistry book series (TOPORGAN, volume 49)


This chapter focuses on the stereo-controlled homologation of chiral boronic esters with chiral lithium carbenoid (lithiation–borylation) as a powerful method for the asymmetric synthesis of many complex molecules. It is highlighted that the potential methodology to create multiple contiguous stereogenic centers on “growing” carbon chains.


1,2-Metallate rearrangement Boronic esters Stereospecific Homologation Lithiated carbamates Total synthesis 


  1. 1.
    Thomas SP, French RM, Jheengut V, Aggarwal VK (2009) Chem Rec 9:24CrossRefGoogle Scholar
  2. 2.
    Watson CG, Unsworth PJ, Leonori D, Aggarwal VK (2014) Lithium–boron chemistry: a synergistic strategy in modern synthesis. Wiley, WeinheimGoogle Scholar
  3. 3.
    Matteson DS (1989) Chem Rev 89:1535CrossRefGoogle Scholar
  4. 4.
    Matteson DS (1995) Reactivity and structure concepts in organic chemistry, vol 32. Springer, BerlinGoogle Scholar
  5. 5.
    Matteson DS (2012) J Org Chem 78:10009CrossRefGoogle Scholar
  6. 6.
    Matteson DS, Man H-W (1996) J Org Chem 61:6047CrossRefGoogle Scholar
  7. 7.
    Aggarwal VK, Fang GY, Ginesta X, Howells DM, Zaja M (2006) Pure Appl Chem 78:215CrossRefGoogle Scholar
  8. 8.
    Hoffmann RW, Nell PG, Leo R, Harms K (2000) Chem Eur J 6:3359CrossRefGoogle Scholar
  9. 9.
    Blakemore PR, Marsden SP, Vater HW (2006) Org Lett 8:773CrossRefGoogle Scholar
  10. 10.
    Blakemore PR, Burge MS (2007) J Am Chem Soc 129:3068CrossRefGoogle Scholar
  11. 11.
    Hoppe D, Marr F, Bruggemann M (2003) Organolithiums. In: Hodgson DM (ed) Enantioselective synthesis, vol 2005. Springer, London, p 2073Google Scholar
  12. 12.
    Beckmann E, Desai V, Hoppe D (2004) Synlett 2275Google Scholar
  13. 13.
    Beckmann E, Hoppe D (2005) Synthesis 217Google Scholar
  14. 14.
    Besong G, Jarowicki K, Kocienski PJ, Sliwinskia E, Boyle FT (2006) Org Biomol Chem 4:2193CrossRefGoogle Scholar
  15. 15.
    Stymiest JL, Dutheuil G, Mahmood A, Aggarwal VK (2007) Angew Chem Int Ed 46:7491CrossRefGoogle Scholar
  16. 16.
    Larouche-Gauthier R, Fletcher CJ, Couto I, Aggarwal VK (2011) Chem Commun 47:12592CrossRefGoogle Scholar
  17. 17.
    Fletcher CJ, Wheelhouse KMP, Aggarwal VK (2013) Angew Chem Int Ed 52:2503CrossRefGoogle Scholar
  18. 18.
    Dutheuil G, Webster MP, Worthington PA, Aggarwal VK (2009) Angew Chem Int Ed 48:6317CrossRefGoogle Scholar
  19. 19.
    Zweifel G, Arzoumanian H, Whitney CC (1967) J Am Chem Soc 89:3652CrossRefGoogle Scholar
  20. 20.
    Althaus M, Mahmood A, Suàrez JR, Thomas SP, Aggarwal VK (2010) J Am Chem Soc 132:4025CrossRefGoogle Scholar
  21. 21.
    Binanzer M, Fang GY, Aggarwal VK (2010) Angew Chem Int Ed 49:4264CrossRefGoogle Scholar
  22. 22.
    Robinson A, Aggarwal VK (2010) Angew Chem Int Ed 49:6673CrossRefGoogle Scholar
  23. 23.
    Robinson A, Aggarwal VK (2012) Org Biomol Chem 10:1795CrossRefGoogle Scholar
  24. 24.
    Lange H, Huenerbein R, Frohlich R, Grimme S, Hoppe D (2007) Chem Asian J 3:78CrossRefGoogle Scholar
  25. 25.
    Lange H, Huenerbein R, Wibbeling B, Frohlich R, Grimme S, Hoppe D (2008) Synthesis 2095Google Scholar
  26. 26.
    Matthew SC, Glasspole BW, Eisenberger P, Crudden CM (2014) J Am Chem Soc 136:5828CrossRefGoogle Scholar
  27. 27.
    Roesner S, Brown CA, Mohiti M, Pulis AP, Rasappan R, Blair DJ, Essafi S, Leonori D, Aggarwal VK (2014) Chem Commun 50:4053CrossRefGoogle Scholar
  28. 28.
    Stymiest JL, Bagutski V, French RM, Aggarwal VK (2008) Nature 456:778CrossRefGoogle Scholar
  29. 29.
    Watson CG, Aggarwal VK (2013) Org Lett 15:1346CrossRefGoogle Scholar
  30. 30.
    Bagutski V, French RM, Aggarwal VK (2010) Angew Chem Int Ed 49:5142CrossRefGoogle Scholar
  31. 31.
    Scott HK, Aggarwal VK (2011) Chem Eur J 17:13124CrossRefGoogle Scholar
  32. 32.
    Sonawane RP, Jheengut V, Rabalakos C, Larouche-Gauthier R, Scott HK, Aggarwal VK (2011) Angew Chem Int Ed 50:3760CrossRefGoogle Scholar
  33. 33.
    Nave S, Sonawane RP, Elford TG, Aggarwal VK (2010) J Am Chem Soc 132:17096CrossRefGoogle Scholar
  34. 34.
    Roesner S, Casatejada JM, Elford TG, Sonawane RP, Aggarwal VK (2011) Org Lett 13:5740CrossRefGoogle Scholar
  35. 35.
    Elford TG, Nave S, Sonawane RP, Aggarwal VK (2011) J Am Chem Soc 133:16798CrossRefGoogle Scholar
  36. 36.
    Aggarwal VK, Ball LT, Carobene S, Connelly RL, Hesse MJ, Partridge BM, Roth P, Thomas SP, Webster MP (2012) Chem Commun 48:9230CrossRefGoogle Scholar
  37. 37.
    Matteson DS, Kim GY (2002) Org Lett 4:2153CrossRefGoogle Scholar
  38. 38.
    Kim GY, Matteson DS (2004) Angew Chem Int Ed 43:3056CrossRefGoogle Scholar
  39. 39.
    Bagutski V, Elford TG, Aggarwal VK (2011) Angew Chem Int Ed 50:1080CrossRefGoogle Scholar
  40. 40.
    Bagutski V, Ros A, Aggarwal VK (2009) Tetrahedron 65:9956CrossRefGoogle Scholar
  41. 41.
    Mlynarski SN, Karns AS, Morken JP (2012) J Am Chem Soc 134:16449CrossRefGoogle Scholar
  42. 42.
    Blair DJ, Fletcher CJ, Wheelhouse KMP, Aggarwal VK (2014) Angew Chem Int Ed 53:5552CrossRefGoogle Scholar
  43. 43.
    Pulis AP, Aggarwal VK (2012) J Am Chem Soc 134:7570CrossRefGoogle Scholar
  44. 44.
    Hoppe D (1984) Angew Chem Int Ed 23:932–948CrossRefGoogle Scholar
  45. 45.
    Krämer T, Schwark J-R, Hoppe D (1989) Tetrahedron Lett 30:7037CrossRefGoogle Scholar
  46. 46.
    Zschage O, Schwark J-R, Hoppe D (1990) Angew Chem Int Ed 29:296CrossRefGoogle Scholar
  47. 47.
    Pulis AP, Fackler P, Aggarwal VK (2014) Angew Chem Int Ed 126:4471CrossRefGoogle Scholar
  48. 48.
    Partridge BM, Chausset-Boissarie L, Burns M, Pulis AP, Aggarwal VK (2012) Angew Chem Int Ed 51:11795CrossRefGoogle Scholar
  49. 49.
    Dreller S, Dyrbusch M, Hoppe D (1991) Synlett 397Google Scholar
  50. 50.
    Hoppe D, Hintze F, Tebben P (1990) Angew Chem Int Ed 29:1422CrossRefGoogle Scholar
  51. 51.
    Beak P, Carter LG (1981) J Org Chem 46:2363CrossRefGoogle Scholar
  52. 52.
    Pulis AP, Blair DJ, Torres E, Aggarwal VK (2013) J Am Chem Soc 135:16054CrossRefGoogle Scholar
  53. 53.
    Beak P, Kerrick ST, Wu S, Chu J (1994) J Am Chem Soc 116:3231CrossRefGoogle Scholar
  54. 54.
    Bertini Gross KM, Jun YM, Beak P (1997) J Org Chem 62:7679CrossRefGoogle Scholar
  55. 55.
    Park YS, Boys ML, Beak P (1996) J Am Chem Soc 118:3757CrossRefGoogle Scholar
  56. 56.
    Coldham I, Patel JJ, Raimbault S, Whittaker DTE, Adams H, Fang GY, Aggarwal VK (2008) Org Lett 10:141CrossRefGoogle Scholar
  57. 57.
    Schmidt F, Keller F, Vedrenne E, Aggarwal VK (2009) Angew Chem Int Ed 48:1149CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2015

Authors and Affiliations

  1. 1.School of ChemistryUniversity of BristolBristolUK

Personalised recommendations