Enantioselective construction of vicinal stereogenic quaternary centers by dialkylation: Practical total syntheses of (+)- and meso-chimonanthine

Angewandte Chemie - International Edition

Volumn 39, Issue 1, 2000, Pages 213-215

  Overman, Larry E ^a   Larrow, Jay F ^a   Stearns, Brian A ^a   Vance, Jennifer M ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Alkaloids; Alkylations; Asymmetric synthesis; Total synthesis

Indexed keywords

EID: 84897607213     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000103)39:1<194::AID-ANIE194>3.3.CO;2-V     Document Type: Article

References (24)

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2. Recent reviews of asymmetric synthesis of quaternary centers; a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401;
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17. 2O at 0 C. Both enantiomers of this intermediate are available from (+)-and ()-tartaric acid: E. A. Mash, K. A. Nelson, S. Van Deusen, S. B. Hemperly in Organic Syntheses, Vol. 68 (Ed.: J. D. White), Wiley, New York, 1990, pp. 92-103.
18. [11]
19. Consistent with this interpretation, stereoselection was eroded in the presence of a sodium-selective cryptand (Kryptofix 221).
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21. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Cristallographic Data Centre as supplementary publication no. CCDC-134670. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road. Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
22. D - + 264.5 (c 1.0 in EtOH).
23. a) A recent survey of stereoselective C - C bond formation cites no examples in sections dealing with alkylation reactions with chiral electrophiles; see D. S. Matteson, Methoden Org. Chem. (Houben-Weyl) 4th ed. 1996, Vol. E21/2, pp. 1077-1118;
24. b) Interconversion of atropisomers of the dienolates derived from 6 is likely to be slow under the alkylation conditions. Whether the 20:1 selectivity arises solely in the initial alkylation step or is enhanced by selective partitioning of the minor diastereomer in the cyclization step has not yet been determined.