Brønsted Acid-Initiated Formal [1,3]-Rearrangement Dictated by β-Substituted Ene-Aldimines

Chanantida Jongwohan; Yasushi Honda; Toshiyasu Suzuki; Takeshi Fujinami; Kiyohiro Adachi; Norie Momiyama

doi:10.1021/acs.orglett.9b01533

Brønsted Acid-Initiated Formal [1,3]-Rearrangement Dictated by β-Substituted Ene-Aldimines

Org Lett. 2019 Jul 5;21(13):4991-4995. doi: 10.1021/acs.orglett.9b01533. Epub 2019 Jun 20.

Authors

Chanantida Jongwohan^{1

2}, Yasushi Honda³, Toshiyasu Suzuki^{1

2}, Takeshi Fujinami¹, Kiyohiro Adachi^{1

4}, Norie Momiyama^{1

2}

Affiliations

¹ Institute for Molecular Science , Okazaki , Aichi 444-8787 , Japan.
² SOKENDAI, The Graduate University for Advanced Studies , Okazaki , Aichi 444-8787 , Japan.
³ West Japan Office , HPC Systems Inc. , 646 Nijohanjikicho , Shimogyo-ku, Kyoto 600-8412 , Japan.
⁴ Department of Applied Chemistry, School of Engineering , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku , Tokyo 111-8656 , Japan.

PMID: 31247769
DOI: 10.1021/acs.orglett.9b01533

Abstract

The rearrangement of ene-aldimines is a useful reaction for affording homoallylic amines. Despite their utilities in synthetic chemistry, the rearrangement for accessing homoallylic amines substituted at the 2-position remains elusive. In this study, the Brønsted acid-initiated formal [1,3]-rearrangement of ene-aldimines was developed to synthesize 2,4,4-substituted homoallylic amines that were otherwise inaccessible previously. Our study reveals an intermolecular pathway in which the rearrangement proceeds via a protonation-mediated 2-azaallenium cation.

Publication types

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