Chan-Lam Amination of Benzylic Secondary and Tertiary Boronic Esters

08 September 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The Cu-catalysed coupling of arylboronic acids with amines, known as the Chan-Lam reaction, is used widely to prepare aryl amines. In contrast, alkyl variants of this reaction, while highly desirable, are underdeveloped. Herein, we report a Chan-Lam coupling reaction of benzylic boronic esters with primary and secondary anilines to form valuable alkyl amine products. Both secondary and tertiary boronic esters can be used as coupling partners, with mono-alkylation of the aniline occurring selectively. This is a rare example of a transition metal-mediated transformation of a tertiary alkylboron reagent. The method is operationally simple and tolerates a broad range of functional groups. Initial investigation into the reaction mechanism suggests that transmetallation from B to Cu occurs through a single electron, rather than a two-electron process.

Keywords

amination methods
Boron
Cu catalysis
Chan-Lam Reaction
Boronic Ester Chemistry

Supplementary materials

Title
Description
Actions
Title
BP amination SI
Description
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.