Highly Enantioselective Inverse-Electron-Demand Hetero-Diels–Alder Reactions of α,β-Unsaturated Aldehydes†
Karl Gademann Dr.
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorDavid E. Chavez
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorEric N. Jacobsen Prof. Dr.
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorKarl Gademann Dr.
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorDavid E. Chavez
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorEric N. Jacobsen Prof. Dr.
Department of Chemistry and Chemical Biology Harvard University Cambridge, MA 02138 (USA) Fax: (+1) 617-496-1880
Search for more papers by this authorThis work was supported by the NIH (GM-59316), with additional support from the Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung (postdoctoral fellowship to K.G.), and the National Science Foundation (predoctoral fellowship to D.E.C.). We are grateful to Dr. R. Staples for carrying out the X-ray crystal structure analysis of 1.
Graphical Abstract
Straightforward access to useful synthetic intermediates is provided by this new method. Simple, α,β-unsaturated aldehydes are excellent substrates in the hetero-Diels–Alder reaction with inverse electron demand, catalyzed by CrIII–Schiff base complexes (see scheme; R1, R2=alkyl or aryl) in the presence of 4-Å molecular sieves and no solvent. The resulting dihydropyrans are obtained in high enantio- (89–98 % ee) and diastereoselectivity (>95 % de) and yield (40–95 %).
Supporting Information
Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2002/z19516_s.pdf or from the author.
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