Catalytic Asymmetric and Stereoselective Synthesis of Vinylcyclopropanes

Abstract

The first sequential catalytic asymmetric carbolithiation reaction of dienyl systems followed by a 1,3-intramolecular elimination leads to (E)- and trans-disubstituted vinylcyclopropanes in moderate to good enantiomeric excesses.

Key words

carbometallation - (-)-sparteine - chirality - vinylcyclopropanes - asymmetric catalysis

References

• 1a Topics in Current Chemistry: Small Ring Compounds in Organic Synthesis I   Vol. 133:  de Meijere A. Springer; Berlin: 1986. 
• 1b Topics in Current Chemistry: Small Ring Compounds in Organic Synthesis II   Vol. 135:  de Meijere A. Springer; Berlin: 1987. 
• 1c Topics in Current Chemistry: Small Ring Compounds in Organic Synthesis III   Vol. 144:  de Meijere A. Springer; Berlin: 1988. 
• 1d Topics in Current Chemistry: Small Ring Compounds in Organic Synthesis IV   Vol. 155:  de Meijere A. Springer; Berlin: 1990. 
• 1e Topics in Current Chemistry: Small Ring Compounds in Organic Synthesis V   Vol. 178:  de Meijere A. Springer; Berlin: 1996. 
• 1f Reissig HU. In The Chemistry of the Cyclopropyl Group   Rappoport Z. Wiley; Chichester: 1987.  p.375 
• 1g Salaün J. Chem. Rev.  1989,  89:  1247 
• 1h Wendisch D. Houben-Weyl, Methoden der Organischen Chemie   Vol. IV/3, 4th ed:  Müller E. Thieme; Stuttgart: 1971. 
• 1i Houben-Weyl, Methoden der Organischen Chemie   Vol. E19b, 4th ed.:  Regitz M. Thieme; Stuttgart: 1989. 
• 1j Houben-Weyl, Methods in Organic Chemistry, Carbocyclic Three-Membered Ring Compounds   de Meijere A. Thieme; Stuttgart: 1997. 
• 2a Charette AB. Marcoux JF. Synlett  1995,  1197 
• 2b Charette AB. Côté B. Marcoux JF. J. Am. Chem. Soc.  1991,  113:  8166 
• 2c Charette AB. Juteau H. J. Am. Chem. Soc.  1994,  116:  2651 
• 2d Denmark SE. O" Connor SP. J. Org. Chem.  1997,  62:  584 
• 3a Davies HML. Huby NJS. Cantrell WR. Olive JL. J. Am. Chem. Soc.  1993,  115:  9468 
• 3b Doyle MP. In Catalytic Asymmetric Synthesis   Ojima I. VCH Publishers; New York: 1993.  Chap. 5.
• 3c Pfaltz A. Acc. Chem. Res.  1993,  26:  339 
• 3d Evans DA. Woerpel KA. Scott MJ. Angew. Chem. Int. Ed. Engl.  1992,  31:  430 
• See: (e) Gross Z. Galili N. Simkhovich L. Tetrahedron Lett.  1999,  40:  1571 ; and references cited therein
• 4a Marek I. J. Chem. Soc. Perkin Trans. 1  1999,  535 
• 4b Norsikian S. Marek I. Klein S. Poisson JF. Normant JF. Chem. Eur. J.  1999,  5:  2055 
• 4c Klein S. Marek I. Poisson JF. Normant JF. J. Am. Chem. Soc.  1995,  117:  8853 
• 5 Paetow M. Kotthaus M. Grehl M. Fröhlich R. Hoppe D. Synlett  1994,  1034 
• For reviews on the use of sparteine in syntheses, see:
• 6a Hoppe D. Hense T. Angew. Chem., Int. Ed. Engl.  1997,  36:  2282 
• 6b Beak P. Basu A. Gallagher DJ. Park JS. Thuyumanavan S. Acc. Chem. Res.  1996,  29:  552 
• 6c Aggarwal VK. Angew. Chem., Int. Ed. Engl.  1994,  33:  175 
• 7 Norsikian S. Marek I. Poisson JF. Normant JF. J. Org. Chem.  1997,  62:  4898 
• 8 Norsikian S. Baudry M. Normant JF. Tetrahedron Lett.  2000,  41:  6575 
• 9a Wong HNC. Hon MY. Tse CW. Yip YC. Tanko J. Hudlicky T. Chem. Rev.  1989,  89:  165 
• 9b Hudlicky T. Becker DA. Fan RL. In Houben-Weyl, Methods of Organic Chemistry   Vol E 17c:  de Meijere A. Thieme; Stuttgart: 1997.  p.p 2538 
• 10a Barrett AGM. Tam W. J. Org. Chem.  1997,  62:  4653 ; and references cited therein
• 10b Kende AS. Mendoza JS. Fujii Y. Tetrahedron  1993,  49:  8015 
• 10c Michelet V. Adiey K. Bulic B. Genet JP. Dujardin G. Rossignol S. Brown E. Toupet L. Eur. J. Org. Chem.  1999,  2885 
• 11a Frey HM. Walsh R. Chem. Rev.  1969,  69:  103 
• 11b de Meijere A. Angew. Chem. Int. Ed. Engl.  1979,  18:  809 
• 11c Andrews GD. Baldwin JE. J. Am. Chem. Soc.  1976,  98:  6705 
• 12a Wender PA. Rieck H. Fuji M. J. Am. Chem. Soc.  1998,  120:  10976 
• 12b Wender PA. Sperandio D. J. Org. Chem.  1998,  63:  4164 
• 12c Wender PA. Husfeld CO. Langkopf E. Langkopf E. Love JA. Pleuss N. Tetrahedron  1998,  54:  7203 
• 12d Davies HML. Stafford DG. Doan BD. Houser JH. J. Am. Chem. Soc.  1998,  120:  3326 
• 12e Binger P. Wedemann P. Kozhushkov SI. de Meijere A. Eur. J. Org. Chem.  1998,  113 
• 13a Bäckvall JE. Vagberg JO. Zercher C. Genet JP. Denis A. J. Org. Chem.  1987,  52:  5430 
• 13b Yan TH. Paquette LA. Tetrahedron Lett.  1982,  23:  3227 
• 13c Krief A. Dumont W. Pasau P. Lecomte P. Tetrahedron  1989,  45:  3039 
• 13d Salaun J. Karkour B. Ollivier J. Tetrahedron  1989,  45:  3151 
• 13e Trost BM. Top. Curr. Chem.  1986,  133:  3 
• 13f Piers E. Jean M. Marrs PS. Tetrahedron Lett.  1987,  28:  5075 
• 13g Hanessian S. Andreotti D. Gomtsyan A. J. Am. Chem. Soc.  1995,  117:  10393 
• 13h Ye SY. Tang Y. Dai LX. J. Org. Chem.  2001,  66:  5717 
• 14a Martin SF. Hom RY. Dwyer MP. Tetrahedron Lett.  1999,  40:  6721 
• 14b Charette AB. Juteau H. Lebel H. Molinaro C. J. Am. Chem. Soc.  1998,  120:  11943 
• 15 Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. 
• 16 Kolodiazhnyi OI. In Phosphorus Ylides   Kolodiazhnyi O. I., Wiley-VCH; Weinheim: 1999. 
• 17 Kluge AF. Untch KG. Fried JH. J. Am. Chem. Soc.  1972,  94:  7827 
• 19 Krief A. Hobe M. Tetrahedron Lett.  1992,  33:  6529 
• 20 Beak P. Anderson DR. Curtis MD. Laumer JM. Pippel DJ. Weisenburger GA. Acc. Chem. Res.  2000,  33:  715 
• 21a Alexakis A. Aujard I. Mangeney P. Synlett  1998,  873 
• 21b Alexakis A. Aujard I. Mangeney P. Synlett  1998,  875 
• 23a Lucet D. Le Gall T. Mioskowski C. Angew. Chem. Int. Ed.  1998,  37:  2581 
• 23b Mangeney P. Alexakis A. Normant JF. Tetrahedron Lett.  1988,  29:  2677 
• 23c Alexakis A. Mangeney P. Marek I. Rose-Munch F. Rose E. Semra A. Roberts F. J. Am. Chem. Soc.  1992,  114:  8288 
• 24 Imai T. Mineta H. Nishida S. J. Org. Chem.  1990,  55:  4986 

18

Typical Experimental Procedure for the Preparation of 13a from 7: A solution of acetal 7 (1 mmol) in hexane (5 mL) was added to the solution of n-butyllithium (3.3 mmol) in hexane in the presence of 10 mol% of (-)-sparteine (based on starting material) at -10 °C over a period of 20 min. When the carbolithiation reaction was complete (as followed by TLC), the orange reaction mixture was rapidly warmed to room temperature and stirred overnight. Then the reaction mixture was cooled to 0 °C, and an aqueous 1 N HCl solution (10 mL) was added. The organic phase was separated, and the aqueous layer was extracted twice with ether (2 × 10 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated under reduced pressure (flask being immerged in an icewater bath). The residue was purified by column chromatography over silica gel (60-120 mesh, hexane) to give the desired compound 13a in 53% yield with an enantiomeric excess of 83%.

22

A large excess of (1R, 2R)-N, N’-dimethyl-1,2-diphenylethanediamine was used in order to avoid any kinetic resolution. No starting material was left (see ref. [19] ).

25

Specific rotations for vinylcyclopropane derivatives: 12a [α]_D ²⁵ = -13.33 (c 0.60, CHCl₃); 12b [α]_D ²⁵ = -11.66 (c 1.2, CHCl₃); 13a [α]_D ²⁵ = -46.6 (c 1.67, CHCl₃); 13b [α]_D ²⁵ = -23.3 (c 1.2, CHCl₃); 14a [α]_D ²⁵ = -25.45 (c 1.12, CHCl₃); 14b [α]_D ²⁵ = -17.5 (c 0.80, CHCl₃); 15a [α]_D ²⁵ = -8.24 (c 1.7, CHCl₃); 15b [α]_D ²⁵ = -7.69 (c 1.04, CHCl₃); 17 [α]_D ²⁵ = -20.0 (c 0.80, CHCl₃).