Enantioselective Assembly of Fully Substituted α‐Amino Allenoates Through a Mannich Addition and Stepwise [3,3]‐σ Rearrangement Sequence DOI Creative Commons

Haoxuan Yuan,

Yi Zhou,

Xiongda Xie

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 12(2)

Published: Nov. 20, 2024

Abstract Chiral fully‐substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly these skeletons using readily available reactants offers advantages but remains challenging. Herein, an asymmetric formal Michael‐type addition alkynyl imines with the key alkylgold intermediates derived situ from N ‐propargylamides is accomplished under gold‐complex chiral quinine‐derived squaramide (QN‐SQA) synergetic catalysis. Control experiments density functional theory (DFT) calculations indicated this cascade reaction involves Mannich‐type stepwise [3,3]‐σ rearrangement sequence, leading to fully substituted α‐amino allenoates, which elusive take multi‐step prepare other methods, high yields excellent enantioselectivity.

Language: Английский

Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates DOI

Yuan Haoxuan,

Ming Bao, Ke-Wei Chen

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5211 - 5218

Published: March 12, 2025

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

Language: Английский

Citations

0
Enantioselective Assembly of Fully Substituted α‐Amino Allenoates Through a Mannich Addition and Stepwise [3,3]‐σ Rearrangement Sequence DOI Creative Commons

Haoxuan Yuan,

Yi Zhou,

Xiongda Xie

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 12(2)

Published: Nov. 20, 2024

Abstract Chiral fully‐substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly these skeletons using readily available reactants offers advantages but remains challenging. Herein, an asymmetric formal Michael‐type addition alkynyl imines with the key alkylgold intermediates derived situ from N ‐propargylamides is accomplished under gold‐complex chiral quinine‐derived squaramide (QN‐SQA) synergetic catalysis. Control experiments density functional theory (DFT) calculations indicated this cascade reaction involves Mannich‐type stepwise [3,3]‐σ rearrangement sequence, leading to fully substituted α‐amino allenoates, which elusive take multi‐step prepare other methods, high yields excellent enantioselectivity.

Language: Английский

Citations

2