Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates

The asymmetric electrophilic amination using azodicarboxylates as the N-source for the construction of the C–N bond has attracted much attention over the past decades. However, the use of in situ formed nucleophilic intermediates, rather than bench-stable reagents, for the asymmetric amination remains elusive and challenging. Herein, we disclose an enantioselective electrophilic amination reaction of in situ generated alkylgold species with azodicarboxylates under a gold complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis, leading to chiral alkylideneoxazolines with a nitrogen-containing tertiary carbon stereocenter in good to high yields and enantioselectivities. Moreover, starting from the same reagents, the oxazoles incorporating an aminomethyl group on the 5-position could be obtained by gold and Brønsted acid relay catalysis via alkylideneoxazoline species. This method offers a complementary approach for the electrophilic amination through interception of in situ formed alkylgold species. With this strategic protocol, further synthetic applications can be envisioned for the catalytic construction of C–C and C–X bonds.