Stereoselective Synthesis of Nitrogen-Containing Compounds from Enamines

Masaharu Sugiura; Takeru Kashiwagi; Mai Ito; Shunsuke Kotani; Makoto Nakajima

doi:10.1021/acs.joc.7b01923

Stereoselective Synthesis of Nitrogen-Containing Compounds from Enamines

J Org Chem. 2017 Oct 20;82(20):10968-10979. doi: 10.1021/acs.joc.7b01923. Epub 2017 Oct 6.

Authors

Masaharu Sugiura¹, Takeru Kashiwagi¹, Mai Ito¹, Shunsuke Kotani¹, Makoto Nakajima¹

Affiliation

¹ Graduate School of Pharmaceutical Sciences and ‡Priority Organization for Innovation and Excellence, Kumamoto University , 5-1 Oe-honmachi, Chuo-ku, Kumamoto 862-0973, Japan.

PMID: 28915033
DOI: 10.1021/acs.joc.7b01923

Abstract

The domino reaction of enamines, electrophiles (N-sulfonylimines, N-tosylisocyanate, or diethyl azodicarboxylate), and trichlorosilane provided trans-amines (trans/cis = > 99:1 to 96:4). Meanwhile, the sequential imino ene-type reaction of enamines and electrophiles/NaBH₃CN reduction afforded cis-amines (trans/cis = 1:>99 to 15:85). The reversal of selectivity is discussed on the basis of diastereofacial selection of the plausible iminium ion intermediates. For the domino reaction of cyclic enamines and cyclic imines, high enantioselectivity (er = 95.7:4.3 to 99.9:0.1) was achieved by utilizing chiral Lewis base catalysts.

Publication types

Research Support, Non-U.S. Gov't