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4. Organocatalytic Enantioselective 1,12‐Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ.

Author

Wang, Xing, Shen, Boming, Liu, Meiwen, Wang, Ziyang, Liu, Chang, Li, Pengfei, Yu, Peiyuan, and Li, Wenjun

Subjects
*QUINONE methides, *DIPHENYL, *PROPARGYL alcohol, *DENSITY functional theory, *PHOSPHORIC acid, *CARBONYL compounds, *ALLENE
Abstract

The chemistry of quinone methides formed in situ has been flourishing in recent years. In sharp contrast, the development and utilization of biphenyl quinone methides are rare. In this study, we achieved a remote stereocontrolled 1,12‐conjugate addition of biphenyl quinone methides formed in situ for the first time. In the presence of a suitable chiral phosphoric acid, alkynyl biphenyl quinone methides were generated from α‐[4‐(4‐hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective 1,12‐conjugate addition with indole‐2‐carboxylates. The strategy enabled the alcohols to serve as efficient allenylation reagents, providing practical access to a broad range of axially chiral allenes bearing a (1,1′‐biphenyl)‐4‐ol unit, which were previously less accessible. Combined with control experiments, density functional theory calculations shed light on the reaction mechanism, indicating that enantioselectivity originates from the nucleophilic addition of alkynyl biphenyl quinone methides. Notably, not only the presence of biphenyl quinone methides as versatile intermediates was confirmed but also organocatalytic enantioselective 1,12‐addition was established. [ABSTRACT FROM AUTHOR]

Published
2024
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7. Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines

Author

Du, Xuan-Yi, Fang, Jia-Heng, Chen, Ji-Jun, Shen, Boming, Liu, Wei-Long, Zhang, Jia-Yong, Ye, Xue-Man, Yang, Ning-Yuan, Gu, Qiang-Shuai, Li, Zhong-Liang, Yu, Peiyuan, and Liu, Xin-Yuan

Abstract

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, the bond formation relies on the interaction between nucleophile-sequestered metal complexes and radicals, limiting the nucleophile scope to sterically uncongested ones. The coupling of sterically congested nucleophiles poses a significant challenge due to difficulties in transmetalation, restricting the reaction generality. Here, we describe a probable outer-sphere nucleophilic attack mechanism that circumvents the challenging transmetalation associated with sterically congested nucleophiles. This strategy enables a general copper-catalyzed enantioconvergent radical N-alkylation of aromatic amines with secondary/tertiary alkyl halides and exhibits catalyst-controlled stereoselectivity. It accommodates diverse aromatic amines, especially bulky secondary and primary ones to deliver value-added chiral amines (>110 examples). It is expected to inspire the coupling of more nucleophiles, particularly challenging sterically congested ones, and accelerate reaction generality.

Published
2024
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20. σ-Bond Migration Assisted Decarboxylative Activation of Vinylene Carbonate in Rh-Catalyzed 4 + 2 Annulation: A Theoretical Study

Author

Shen, Boming, Liu, Song, Zhu, Lei, Zhong, Kangbao, Liu, Fenru, Chen, Haohua, Bai, Ruopeng, and Lan, Yu

Abstract

As a C2 synthon, vinylene carbonate has been used instead of acetylene in transition-metal catalyzed-coupling reactions. In this study, the mechanism of the vinylene carbonate activation mode for the Rh(III)-catalyzed 4 + 2 annulation of benzamide and vinylene carbonate reaction is proposed, and it was investigated by DFT with the M06 density functional. The computational results show that the proposed reaction pathway, which includes the insertion of vinylene carbonate into an Rh–C bond, decarboxylation of the seven-membered rhodacycle intermediate, protonation of the ketonate rhodium intermediate, deprotonation of the benzamide, and catalyst regeneration, is the most favorable pathway. The 1,2-rhodium migration process can assist decarboxylative activation of vinylene carbonate, which is the rate-determining step in the catalytic cycle. The IRC calculation clearly revealed a quasi-synchronized process to directly afford a cyclic ketonate rhodium intermediate by the release of carbon dioxide.

Published
2024
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