Abstract
Compounds bearing both boryl and amino groups are highly valuable synthons in organic
synthesis. However, while enantioselective 1,1- and 1,2-borylamination reactions have
been developed, processes enabling distal borylamination have rarely been investigated.
Here, we present an enantioselective 1,4-borylamination reaction, achieved through
a copper-catalyzed cascade hydroborylation and hydroamination of arylidenecyclopropanes.
This four-component reaction provides direct access to enantioenriched 4-aminoalkylboronate
products with high chemo-, site-, and enantioselectivity. The versatility of these
products was demonstrated through their broad transformations and extensive applications
in the synthesis of various drug core structures. Additionally, preliminary mechanistic
studies were conducted to investigate the reaction pathway, intermediates, and high
chemo- and site-selectivity.
Key words
arylidenecyclopropane - 1,4-borylamination, borylative functionalization - copper
catalysis - copper hydride - asymmetric synthesis
