N-Methyl Allylic Amines from Allylic Alcohols by Mitsunobu Substitution Using N-Boc Ethyl Oxamate

Abstract

We report the practical, scalable synthesis of a range of N-methyl allylic amines. Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N-Boc ethyl oxamate to deliver the corresponding N-Boc allylic amines, including in enantiopure form via stereospecific substitution. Subsequent N-methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts. This method solves the problem of converting commercially available alcohols into often volatile N-methyl allylic amines, many of which have limited commercial availability.

A Chemoselective Polarity‐Mismatched Photocatalytic C(sp3)−C(sp2) Cross‐Coupling Enabled by Synergistic Boron Activation**

“…The research data supporting this publication can be accessed at https://doi.org/10.17630/33380f7f-28cd-45b8-b55b-dd6b83651e89. The authors have cited additional references within the Supporting Information [50–157] …”

Photocatalytic C–N bond construction toward high-value nitrogenous chemicals

“…These compounds have been used to construct N-containing compounds. [91][92][93][94] The previous catalytic methods (e.g., thermocatalysis and electrocatalysis) have made (c) A phosphine-mediated dual catalytic system is composed of a photoredox catalytic cycle and a cobalt catalytic cycle. The photoredox catalytic cycle absorbs light and excites the activator (e.g., phosphine), while the cobalt catalytic cycle activates the photoredox catalytic cycle and abstracts electrons to generate acyl cations to promote the reaction toward the amide formation.…”

“…These compounds have been used to construct N-containing compounds. 91–94 The previous catalytic methods ( e.g. , thermocatalysis and electrocatalysis) have made great advancements in the catalytic activation of C–O/N–O bonds to form C–N bonds.…”