Stereoinversion of tertiary alcohols to tertiary

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Presentation transcript:

Stereoinversion of tertiary alcohols to tertiary alkyl isonitriles and amines Sergey V. Pronin, Christopher A. Reiher, Ryan A. Shenvi The Scripps Research Institute, La Jolla, California. Nature 501, 2013, 195–199.

Ryan A. Shenvi B.S in chemistry at Penn State with Prof. Raymond L. Funk Ph.D. from The Scripps research Institute with Prof. Phil S. Baran Postdoctoral fellowship in Harvard University with Prof. Elias J. Corey Assistant Professor (2010 - ), Department of Chemistry, The Scripps Research Institute. Research Interests: Total synthesis of terpenes, Alkaloids and natural products targeting neglected tropical diseases

Isonitrile containing secondary terpenoid metabolites

Common methods to access isonitriles

tert-Isonitrile synthesis in Natural products

A direct conversion of alcohols to isonitriles Kitano, Y.; Kazuhiro, C. Tada, M.; Tet. Lett. 1997 39, 1911-1912

Lewis acid modification

Lewis acid screening

Lewis acid modification

Substrate Scope

Substrate Scope

Transformations of formed isonitriles

Limitations

Mechanistic rationale

Increase in fluorination of the substrate ester has an effect on the selectivity towards inversion Use of TMSOTf instead of Sc(OTf)3 did promote any reaction. Addition of 2-6-di-t-butyl pyridine (3:1 with catalyst) did not inhibit product formation, which excludes Bronsted acid catalysis. Addition of stoichiometic TMSOTf did not affect the reaction Reaction seems to be unique to TMSCN as nucleophile/solvent No reaction when MeCN is used as nucleophile, TMSN3 and TMSSCN gave complex mixtures

Conclusions The methodology can be used for Stereoslective conversion of 3 o alcohols to isonitriles and amines Is chemoselective to 3 o alcohols in the presence of 1 o and 2 o alcohols Works best with minmally branched acylic alcohols and conformationally inflexible alicyclic alcohols

Other examples from literature for SN2 at tert-center