Home
  >  
Section 46
  >  
Chapter 45,029

A Convergent Strategy for the Asymmetric Synthesis of Enantiomerically Pure Bicyclic Compounds by Using a Silicon-Directed Cycloaddition Reaction: The Synthesis of Enantiomerically Pure Bicyclo

Adam; Ghosez; Houk

Angewandte Chemie 38(18): 2728-2730

1999

ISSN/ISBN: 1433-7851
PMID: 10508362
DOI: 10.1002/(sici)1521-3773(19990917)38:18<2728::aid-anie2728>3.0.co;2-0
Accession: 045028111
Download citation:  
Text
  |  
BibTeX
  |  
RIS
An asymmetric allylmetalation followed by a silicon-stereodirected cycloaddition gives enantiomerically pure bicyclic compounds. The synthesis of enantiopure 1 (see scheme) in a yield of 65-74 %, 93 % ee, and >98 % de provides an illustration of the efficacy of the method. The preferential formation of 1 rather than its diastereoisomer (32:1), during the cycloaddition step, matches the result predicted by RHF and density functional theory studies.

PDF emailed within 0-6 h: $19.90




Related References

Bräse, S.; Schömenauer, S.; McGaffin, G.; Stolle, A.; de Meijere, A. 1996: Versatile Synthesis of Enantiomerically Pure 2-Alkoxy-1-Ethynylcyclopropanes and their Application in the Synthesis of Enantiomerically Pure Bicyclo-[3.3.0]oct-1-en-3-ones Chemistry 2(5): 545-555
Aggarwal, V.K.; Evans, G.; Moya, E.; Dowden, J. 1992: Chiral, bisfunctionalization of substrates : a powerful strategy for the asymmetric synthesis of C2 compounds and its application to the synthesis of enantiomerically pure trans-1,3-dithiane 1,3-dioxide Journal of Organic Chemistry 57(24): 6390-6391
Taghizadeh, M.J.; Arvinnezhad, H.; Samadi, S.; Jadidi, K.; Javidan, A.; Notash, B. 2012: Synthesis of new enantiomerically pure spirooxindolopyrrolizidines via a three-component asymmetric 1,3-dipolar cycloaddition reaction of azomethine ylides derived from isatin Tetrahedron Letters 53(38): 5148-5150
Aggarwal, V.K.; Evans, G.; Moya, E.; Dowden, J. 1992: Chiral bisfunctionalization of substrates: a powerful strategy for the asymmetric synthesis of C2 symmetric compounds and its application to the synthesis of enantiomerically pure trans-1,3-dithiane 1,3-dioxide The Journal of Organic Chemistry 57(24): 6390-6391
Karlsson, S.; Högberg, H. 2001: Synthesis of enantiomerically pure 4-substituted pyrrolidin-3-ols via asymmetric 1,3-dipolar cycloaddition Tetrahedron: Asymmetry 12(14): 1977-1982
Noonan, G.M.; Cobley, C.J.; Lebl, T.; Clarke, M.L. 2010: Asymmetric hydroformylation of an enantiomerically pure bicyclic lactam: efficient synthesis of functionalised cyclopentylamines Chemistry 16(43): 12788-12791
Snyder, L.; Meyers, A.I. 1993: Synthesis of enantiomerically pure hydrinden-2-ones and benz inden-2-ones via asymmetric alkylations of chiral bicyclic lactams Journal of Organic Chemistry 58(26): 7507-7515
Oppolzer, W.; Blagg, J.; Rodriguez, I.; Walther, E. 1990: Bornanesultam-directed asymmetric synthesis of crystalline, enantiomerically pure syn aldols Journal of the American Chemical Society 112(7): 2767-2772
Quinkert, G. 1988: Enantiomerically pure target compounds by asymmetric synthesis Szantay, C (Ed ) Chemistry And Biotechnology Of Biologically Active Natural Products; Fourth International Conference, Budapest, Hungary, August 10-14, 1987 Xi+402p Akademiai Kiado: Budapest, Hungary Illus 111-132
Hopper, A.T.; Witiak, D.T. 1995: Synthesis of Enantiomerically Pure Stereogenically Labile 4-Aryl-2-hydroxytetronic Acids from Enantiomerically Pure Silyl-Protected Mandelaldehydes: aci-Reductone Analogs of Propionic Acid Nonsteroidal Anti-inflammatory Agents The Journal of Organic Chemistry 60(11): 3334-3341
Myers, A.G.; Widdwoson, K.L. 1990: A silicon-directed aldol condensation. Synthesis of enantiomerically pure anti aldols Journal of the American Chemical Society 112(26): 9672-9674
Nelson, T.D.; Meyers, A.I. 1994: The Asymmetric Ullmann Reaction. 2. the Synthesis of Enantiomerically Pure C2-Symmetric Binaphthyls The Journal of Organic Chemistry 59(9): 2655-2658
Nelson, T.D.; Meyers, A.I. 1994: The asymmetric Ullmann reaction. II: The synthesis of enantiomerically pure C2-symmetric binaphthyls Journal of Organic Chemistry 59(9): 2655-2658
Harwood, L.M.; Lilley, I.A. 1996: Consecutive Intramolecular Azomethine Ylid Cycloaddition - Pummerer Rearrangement as a Strategy for the Synthesis of Enantiomerically Pure 5-(Hydroxymethyl)prolines Synlett 1996(10): 1010-1012
Udry, G.A.O.; Repetto, E.; Vega, D.R.; Varela, O. 2017: Synthesis of Highly Substituted and Enantiomerically Pure 2,3,4-Tris(hydroxyalkyl)pyrrolidines Using a 1,3-Dipolar Cycloaddition Reaction as Key Step ChemistrySelect 2(17): 4774-4778
Soloshonok, V.A.; Cai, C.; Hruby, V.J. 2000: A Practical Asymmetric Synthesis of Enantiomerically Pure 3-Substituted Pyroglutamic Acids and Related Compounds Angewandte Chemie 112(12): 2256-2259
Soloshonok, V.A.; Cai, C.; Hruby, V.J. 2000: A Practical Asymmetric Synthesis of Enantiomerically Pure 3-Substituted Pyroglutamic Acids and Related Compounds Angewandte Chemie International Edition 39(12): 2172-2175
Diedrichs, N.; Westermann, B. 1999: Synthesis of Enantiomerically Pure Bicyclic Lactams Synlett 7: 1127-1129
Shi-Hui, H.; Hirakawa, T.; Fukuba, T.; Hayase, S.; Kawatsura, M.; Itoh, T. 2007: Synthesis of enantiomerically pure cycloalkenols via combination strategy of enzyme-catalyzed reaction and RCM reaction Tetrahedron: Asymmetry 18(20): 2484-2490
Abele, S.; Inauen, R.; Spielvogel, D.; Moessner, C. 2012: Scalable synthesis of enantiomerically pure bicyclo[2.2.2]octadiene ligands Journal of Organic Chemistry 77(10): 4765-4773