Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift DOI

Jianfei Ge,

Xi‐Zhang Zou,

Xinru Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

Language: Английский

Enantioselective and Diastereoselective C–H Alkylation of Benzamides: Synergized Axial and Central Chirality via a Single Stereodetermining Step DOI
Jinlei Wang, Haohua Chen,

Lingheng Kong

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9151 - 9158

Published: July 9, 2021

In this report, distally disposed axial and central chirality has been installed in a synergistic fashion via rhodium-catalyzed C–H alkylation of benzamides using N-arylmaleimide as the alkylating reagent, which enantio- diastereo-determining steps are merged into single one. The coupling system features mild reaction conditions, broad substrate scope, excellent diastereoselectivity. chiral induction enabled by judicious choice rhodium cyclopentadienyl catalyst that serves to control both orientation olefin unit prochiral C–N bond.

Language: Английский

Citations

64
Recent advances in iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands DOI
Takahiro Sawano, Ryo Takeuchi

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(13), P. 4100 - 4112

Published: Jan. 1, 2022

This minireview describes the recent progress of iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands realizing highly carbon–carbon and carbon–heteroatom bond formation.

Language: Английский

Citations

47
Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction DOI
Jia‐Hao Xie,

Yi‐Ming Hou,

Zuolijun Feng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 4, 2023

Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition dialkylzinc reagents to cyclic enones with iridium-catalyzed allylic substitution reaction. Good excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction adjacent (1,2-position) reported in literature, current reaction achieve nonadjacent (1,3-position) proper combination two chiral catalysts different enantiomers.

Language: Английский

Citations

34
Expanding Reaction Profile of Allyl Carboxylates via 1,2-Radical Migration (RaM): Visible-Light-Induced Phosphine-Catalyzed 1,3-Carbobromination of Allyl Carboxylates DOI
Gaoyuan Zhao, Sang-Hyun Lim, Djamaladdin G. Musaev

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8275 - 8284

Published: April 5, 2023

Allyl carboxylates are useful synthetic intermediates in a variety of organic transformations, including catalytic nucleophilic/electrophilic allylic substitution reactions and 1,2-difunctionalization reactions. However, the 1,3-difunctionalization allyl remains elusive. Herein, we report first photoinduced, phosphine-catalyzed 1,3-carbobromination carboxylates, affording range valuable substituted isopropyl (sIPC). The transformation has broad functional group tolerance, is amenable to late-stage modification complex molecules gram-scale synthesis, expands reaction profiles phosphine catalysis. Preliminary experimental computational studies suggest non-chain-radical mechanism involving formation an electron donor-acceptor complex, 1,2-radical migration (RaM), Br-atom transfer processes. We anticipate that 1,2-RaM reactivity radical will both serve as platform for development new transformations synthesis.

Language: Английский

Citations

29
Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift DOI

Jianfei Ge,

Xi‐Zhang Zou,

Xinru Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

Language: Английский

Citations

27