Skip to main content
Log in

New 1,3-amino alcohols derived from enantiopure bridgehead β-aminobicyclo[2.2.2]oct-5-ene-2-carboxylic acids

  • Original Article
  • Published:
Amino Acids Aims and scope Submit manuscript

Abstract

Constrained enantiopure bicyclic β-amino acids derived from the asymmetric Diels–Alder reaction of the (R)-benzyl-4-(3-acryloyloxy-4,4-dimethyl-2-oxopyrrolidin-1-yl)-benzoate and the 1-(benzyloxycarbonylamino)cyclohexadiene provide original templates for the construction of new rigid enantiopure 1,3-amino alcohols.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Scheme 1
Scheme 2
Scheme 3

Similar content being viewed by others

References

  • Ager DJ, Prakash I, Schaad DR (1996) 1, 2-Amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis. Chem Rev 96:835–876

    Article  PubMed  CAS  Google Scholar 

  • Akkari R, Calmès M, Escale F, Iapichella J, Rolland M, Martinez J (2004) (R)- or (S)-4-(3-hydroxy-4, 4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid as a new chiral auxiliary for solid phase asymmetric Diels–Alder reactions. Tetrahedron Asymmetr 15:2515–2525

    Article  CAS  Google Scholar 

  • Balazs AS, Szakonyi Z, Fülöp F (2007) Synthesis of alicyclic N-substituted 1, 3-aminoalcohols via 1, 3-oxazines. J Heterocyclic Chem 44:403–406

    Article  CAS  Google Scholar 

  • Barluenga J, Viado AL, Aguilar E, Fustero S, Olano B (1993) 1, 3-Amino alcohols from 4-amino-1-azadienes. Diastereo- and enantioselective approach to the four diastereoisomers of the N-terminal amino acid component of nikkomycins B and BX. J Org Chem 58:5972–5975

    Article  CAS  Google Scholar 

  • Bartoli G, Cimarelli C, Marcantoni E, Palmieri G, Petrini M (1994) Chemo- and diastereoselective reduction of beta-enamino esters: a convenient synthesis of both cis- and trans-γ-amino alcohols and β-amino esters. J Org Chem 59:5328–5335

    Article  CAS  Google Scholar 

  • Binder CM, Bautista A, Zaidlewicz M, Krzemiński MP, Oliver A, Singaram B (2009) Stereoselectivity in the dialkylzinc reaction using (−)-β-pinene derived amino alcohol chiral auxiliaries. J Org Chem 74:2337–2343

    Article  PubMed  CAS  Google Scholar 

  • Blaser HU (1992) The chiral pool as a source of enantioselective catalysts and auxiliaries. Chem Rev 92:935–952

    Article  CAS  Google Scholar 

  • Calmès M, Didierjean C, Martinez J, Songis O (2005) (R)-(4-(Benzyloxycarbonylphenyl)-3-hydroxy-4, 4-dimethyl-2-pyrrolidinone) acrylate derivative as a chiral dienophile for the synthesis of enantiopure 2-aminocyclohexane carboxylic acids. Tetrahedron Asymmetr 16:2173–2178

    Article  Google Scholar 

  • Corey EJ, Helal CJ (1998) Reduction of carbonyl compounds with chiral oxazaborolidine catalysts: A new paradigm for enantioselective catalysis and a powerful new synthetic sethod. Angew Chem Int Ed Engl 37:1986–2012

    Article  CAS  Google Scholar 

  • Corey EJ, Bakshi RK, Shibata S (1987) Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines. Mechanism and synthetic implications. J Am Chem Soc 109:5551–5553

    Article  CAS  Google Scholar 

  • Delair P, Einhorn C, Einhorn J, Luche JL (1994) Synthesis of beta-amino alcohols derived from l-valine. J Org Chem 59:4680–4682

    Article  CAS  Google Scholar 

  • Deloux L, Screbnik M (1993) Asymmetric boron-catalyzed reactions. Chem Rev 93:763–784

    Article  CAS  Google Scholar 

  • Didier E, Loubinoux B, Ramos Tombo GM, Rihs G (1991) Chemo-enzymatic synthesis of 1, 2- and 1, 3-aminoalcohols and their use in the enantioselective reduction of acetophenone and anti-acetophenone oxime methyl ether with borane. Tetrahedron 47:4941–4958

    Article  CAS  Google Scholar 

  • Fülöp F (2001) The chemistry of 2-aminocycloalkanecarboxylic acids. Chem Rev 101:2181–2204

    Article  PubMed  Google Scholar 

  • Fülöp F, Szakonyi Z, Bernath G, Sohar P (1997) Saturated heterocycles: synthesis of 2, 4-dioxo and 4-oxo-2-thioxo derivatives of octahydrocyclopenta[d]pyrimidines. J Heterocyclic Chem 34:1211–1214

    Article  Google Scholar 

  • Garcia Martinez A, Teso Vilar E, Garcıa Fraile A, de la Moya Cerero S, Martinez Ruiz P, Chicharro Villas P (2002) Bridgehead-norbornane-derived β-amino alcohol catalysts: structural factors influencing the chirality transfer. Tetrahedron Asymmetr 13:1–4

    Article  CAS  Google Scholar 

  • Gyonfalvi S, Szakonyi Z, Fülöp F (2003) Synthesis and transformation of novel cyclic β-amino acid derivatives from (+)-3-carene. Tetrahedron Asymmetr 14:3965–3972

    Article  CAS  Google Scholar 

  • Hobuss D, Baro A, Laschat S, Frey W (2008) Catalytic enantioselective borane reduction of arylketones with pinene-derived amino alcohols. Tetrahedron 64:1635–1640

    Article  CAS  Google Scholar 

  • Khalil EM, Subasinghe NL, Johnson RL (1996) An efficient and high yield method for the N-tert-butyloxycarbonyl protection of sterically hindered amino acids. Tetrahedron Lett 37:3441–3444

    Article  CAS  Google Scholar 

  • Kiss L, Fülöp F (2009) Selective syntheses of functionalized cyclic β-amino acids via transformation of the ring C-C double bonds. Synlett 9:1302–1314

    Google Scholar 

  • Kiss L, Forró E, Fülöp F (2009) Synthesis of carbocyclic β-amino acids. In: Hughes AB (ed) Amino acids, peptides and proteins in organic chemistry: origins and synthesis of amino acids, vol 1. Wiley-VCH, Weinheim, pp 367–409

    Google Scholar 

  • Kitamura M, Suga S, Kawai K, Noyori R (1986) Catalytic asymmetric induction. Highly enantioselective addition of dialkylzincs to aldehydes. J Am Chem Soc 108:6071–6072

    Article  PubMed  CAS  Google Scholar 

  • Kivelä H, Klika KD, Szabo A, Stajer G, Pihlaja K (2003) Structures of saturated 5H-pyrrolo[1,2-a][3,1]benzoxazin-1(2H)-ones prepared from 4-oxopentanoic acid and cyclic amino alcohols. Eur J Org Chem 1879–1886

  • Kivelä H, Zalan Z, Tahtinen P, Sillanpää R, Fülöp F, Pihlaja K (2005) Synthesis and conformational analysis of saturated 3, 1, 2-benzoxazaphosphine 2-oxides. Eur J Org Chem 9:1189–1200

    Article  Google Scholar 

  • Kochi T, Tang TP, Ellman JA (2003) Development and application of a new general method for the asymmetric synthesis of syn- and anti-1, 3-amino alcohols. J Am Chem Soc 125:11276–11282

    Article  PubMed  CAS  Google Scholar 

  • Kossenjans M, Martens J (1998) Synthesis of C 2-symmetrical bis-β-amino alcohols from (R)-cysteine and their application in enantioselective catalysis. Tetrahedron Asymmetr 9:1409–1417

    Article  CAS  Google Scholar 

  • Kossenjans M, Martens J (1999) Highly stereoselective synthesis of 1, 3-aminoalcohols via Mannich reactions. Tetrahedron Asymmetr 10:3409–3416

    Article  CAS  Google Scholar 

  • Krzemiński MP, Wojtczak A (2005) Chiral terpene auxiliaries Part 1: Highly enantioselective reduction of ketones with borane catalyzed by an oxazaborolidine derived from (-)-β-pinene. Tetrahedron Lett 46:8299–8302

    Article  Google Scholar 

  • Krzemiński MP, Zaidlewicz M (2003) Asymmetric reduction of ketoxime derivatives and N-alkylketimines with borane-oxazaborolidine adducts. Tetrahedron Asymmetr 14:1463–1466

    Article  Google Scholar 

  • Laczkowski K, Kmieciak A, Kozakiewicz A (2009) Stereoselective synthesis of new monoterpene β-amino alcohols. Tetrahedron Asymmetr 20:1487–1492

    Article  CAS  Google Scholar 

  • Lait SM, Rankic DA, Keay BA (2007) 1, 3-Aminoalcohols and their derivatives in asymmetric organic synthesis. Chem Rev 107:767–796

    Article  PubMed  CAS  Google Scholar 

  • Li X, Yeung CH, Chan ASC, Yang TK (1999) New 1, 3-amino alcohols derived from ketopinic acid and their application in catalytic enantioselective reduction of prochiral ketones. Tetrahedron Asymmetr 10:759–763

    Article  CAS  Google Scholar 

  • Masui M, Shiori T (1998) Stereoselective synthesis of 1, 2-amino alcohols by asymmetric borane reduction of α-oxoketoxime ethers. Tetrahedron Lett 39:5195–5198

    Article  CAS  Google Scholar 

  • McGeary RP (1998) Facile and chemoselective reduction of carboxylic acids to alcohols using BOP reagent and sodium borohydride. Tetrahedron Lett 39:3319–3322

    Article  CAS  Google Scholar 

  • Murai T, Sano H, Kawai H, Aso H, Shibahara F (2005) N-Thioacyl-1, 3-amino alcohols: synthesis via ring-opening of oxiranes with thioamide dianions and applications as key intermediates leading to stereochemically defined 5, 6-dihydro-4H–1, 3-oxazines and 1, 3-amino alcohols. J Org Chem 70:8148–8153

    Article  PubMed  CAS  Google Scholar 

  • Oliveira L, Costa V (2004) An efficient synthesis of enantiopure (+)- and (−)-syn-1, 3-amino alcohols with the norbornane framework and their application in the asymmetric addition of ZnEt2 to benzaldehyde. Tetrahedron Asymmetr 15:2583–2590

    Article  Google Scholar 

  • Park K-H, Kurth MJ (2002) Cyclic amino acid derivatives. Tetrahedron 58:8629–8659

    Article  CAS  Google Scholar 

  • Raghavan S, Rajender A, Joseph SC, Rasheed MA, Kumar KR (2004) Regio- and stereoselective synthesis of 1, 3-aminoalcohol derivatives from allylamine derivatives via internal sulfinyl group participation. Tetrahedron Asymmetr 15:365–379

    Article  CAS  Google Scholar 

  • Reetz MT, Drewes MW, Schmitz A (1987) Stereoselective synthesis of β-amino alcohols from optically active α-amino acids. Angew Chem Int Ed Engl 26:1141–1143

    Article  Google Scholar 

  • Scarpi D, Occhiato EG, Guarna A (2009) Asymmetric addition of diethylzinc to aldehyde catalyzed by a camphor-derived β-amino alcohol. Tetrahedron Asymmetr 20:340–350

    Article  CAS  Google Scholar 

  • Songis O, Géant PY, Sautrey G, Martinez J, Calmès M (2008) Asymmetric Diels-Alder reaction of nonracemic acrylate bound to Rink resin with some aminodienes: a comparison of these reactions to their solution state analogues. Eur J Org Chem 308–318

  • Songis O, Didierjean C, Martinez J, Calmès M (2007) Asymmetric Diels-Alder cycloaddition of 1-aminocyclohexadiene to chiral acrylate: Synthesis of enantiopure bridgehead aminobicyclo[2.2.2]octane-2-carboxylic acid derivatives. Eur J Org Chem 3166–3172

  • Songis O, Didierjean C, Martinez J, Calmès M (2008b) The iodolactone approach to enantiopure oxiranes of constrained chiral cyclic β-amino acids. Tetrahedron Asymmetr 19:2135–2139

    Article  CAS  Google Scholar 

  • Szakonyi Z, Balazs A, Martinek TA, Fülöp F (2006) Enantioselective addition of ZnEt2 to aldehyde catalyzed by γ-amino alcohols derived from (+)- and (−)-α-pinène. Tetrahedron Asymmetr 17:199–204

    Article  CAS  Google Scholar 

  • Wu ZL, Wu HL, Wu PY, Uang BJ (2009) N-Substituent effects on the diethylzinc addition to benzaldehyde catalyzed by bicyclic 1, 4-aminoalcohols. Tetrahedron Asymmetr 20:1556–1560

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the CNRS and the MESR for their financial support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Monique Calmès.

Rights and permissions

Reprints and permissions

About this article

Cite this article

André, C., Calmès, M., Escale, F. et al. New 1,3-amino alcohols derived from enantiopure bridgehead β-aminobicyclo[2.2.2]oct-5-ene-2-carboxylic acids. Amino Acids 43, 415–421 (2012). https://doi.org/10.1007/s00726-011-1097-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00726-011-1097-6

Keywords

Navigation