Synthesis of Enantiomerically Pure (α-Phenylalkyl)amines with Substituents at the ortho Position through Diastereoselective Radical Alkylation Reaction of Sulfinimines

The alkyl radical (R1) addition reaction to ortho‐X‐substituted N‐(benzylidene)‐2‐methylpropane‐2‐sulfinamides (X = Br, CN, CO2Me, OH and OMe) is highly diastereoselective, regardless of the electronic properties of the X group and the size of R1. Easy removal of the sulfinyl group provides the titl...

Full description

Saved in:
Bibliographic Details
Published in:European journal of organic chemistry 2014-08, Vol.2014 (24), p.5265-5272
Main Authors: Fernández-Salas, José A., Rodríguez-Fernández, M. Mercedes, Maestro, M. Carmen, García-Ruano, José L.
Format: Article
Language:English
Subjects:
Chiral auxiliaries
Diastereoselectivity
Radical reactions
Sulfin­imines
Synthetic methods
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The alkyl radical (R1) addition reaction to ortho‐X‐substituted N‐(benzylidene)‐2‐methylpropane‐2‐sulfinamides (X = Br, CN, CO2Me, OH and OMe) is highly diastereoselective, regardless of the electronic properties of the X group and the size of R1. Easy removal of the sulfinyl group provides the title compounds in enantiomerically pure form. This two‐step sequence has been successfully applied to the preparation of primary α‐(tert‐butyl)‐ortho‐hydroxy‐ and ‐ortho‐methoxybenzylamines, as well as the 3‐isopropyl‐substituted isoindolin‐1‐one. ortho‐Substituted N‐(tert‐butylsulfinyl)benzaldimines are excellent acceptors in the intermolecular addition reactions of alkyl radicals. Easy removal of the sulfinyl group affords enantiopure α‐branched amines. This short two‐step sequence has been successfully applied to prepare ortho‐hydroxy‐ and ortho‐methoxybenzylamines, which are widely used as building blocks in chiral catalysis.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201402355