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. 2013 Feb 20;135(7):2478-81.
doi: 10.1021/ja312311k. Epub 2013 Feb 11.

Unstabilized azomethine ylides for the stereoselective synthesis of substituted piperidines, tropanes, and azabicyclo[3.1.0] systems

Michael A Ischay  1 , Michael K Takase, Robert G Bergman, Jonathan A Ellman
Affiliations

Unstabilized azomethine ylides for the stereoselective synthesis of substituted piperidines, tropanes, and azabicyclo[3.1.0] systems

Michael A Ischay et al. J Am Chem Soc. .

Abstract

Acid treatment of densely substituted 2-silyl-1,2-dihydropyridines provides a new and convenient entry to reactive azomethine ylides that can (1) be protonated and reduced with high stereoselectivity to give piperidines, (2) participate in [3 + 2] dipolar cycloaddition to give tropanes, and (3) undergo a Nazarov-like 6-π electrocyclization that upon reduction give 2-azabicyclo[3.1.0] systems.

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Figures

Scheme 1
Scheme 1
Rapid entry into substituted piperidine, tropane and 2-azabicyclo[3.1.0] frameworks
Scheme 2
Scheme 2
Proposed mechanistic pathways
Scheme 3
Scheme 3
Nazarov-like electrocyclization
See this image and copyright information in PMC

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