Enantioselective 1,4-Borylamination Enabled by Copper Catalysis DOI
Bo Su, Yu‐Jie Zhu

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

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

Language: Английский

Enantioselective 1,4-Borylamination via Copper-Catalyzed Cascade Hydroborylation and Hydroamination of Arylidenecyclopropanes DOI

Yu-Shen Zhu,

Yuecong Guo, Yingying Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32283 - 32291

Published: Nov. 13, 2024

Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, natural products, but their catalytic enantioselective synthesis remains rarely explored. We report the first 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation hydroamination of arylidenecyclopropanes. This combines four readily available components in highly chemo-, site-, fashion (>20:1 r.r. up to 99% ee), yielding diverse array synthetically valuable enantioenriched 4-amino alkylboronates. The versatile utility these products is highlighted by transformations wide applications pharmaceutical discovery. Preliminary mechanistic studies were conducted elucidate operative pathway, intermediates, origins its high chemo- site-selectivity.

Language: Английский

Citations

6
Enantioselective 1,4-borylative amination DOI

Yu-Shen Zhu,

Yingying Zhu, Yuecong Guo

et al.

Trends in Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Recent advances in allylation of chiral secondary alkylcopper species DOI Creative Commons

Min‐Jae Kim,

G.N. Kim,

D.H. Kim

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 639 - 658

Published: March 20, 2025

The transition-metal-catalyzed asymmetric allylic substitution represents a pivotal methodology in organic synthesis, providing remarkable versatility for complex molecule construction. Particularly, the generation and utilization of chiral secondary alkylcopper species have received considerable attention due to their unique properties stereoselective substitution. This review highlights recent advances copper-catalyzed reactions with species, encompassing several key strategies generation: stereospecific transmetalation organolithium organoboron compounds, copper hydride catalysis, enantiotopic-group-selective transformations 1,1-diborylalkanes. Detailed mechanistic insights into stereochemical control current challenges this field are also discussed.

Language: Английский

Citations

0
Enantioselective Borylative Functionalization of Internal Alkenes: A Platform for Constructing Vicinal Stereocenters† DOI
Yu‐Jie Zhu, Jiaxin Li, Haotian Zhao

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(24), P. 3588 - 3604

Published: Nov. 1, 2024

Comprehensive Summary Vicinal stereogenic centers are ubiquitous structural scaffolds in both natural products and synthetic compounds, yet their enantioselective construction remains a significant challenge organic synthesis. Organoboron compounds of paramount importance chemistry due to ability undergo facile transformations, yielding diverse essential chemical bonds such as carbon‐carbon, carbon‐oxygen, carbon‐nitrogen, carbon‐halogen bonds. Transition‐metal‐catalyzed asymmetric borylative functionalizations internal alkenes offer promising strategy for the installation two adjacent chiral across carbon‐carbon By leveraging versatile transformations newly introduced boryl unit, this approach holds great potential expanding diversity vicinal scaffolds. In concise review, we aim highlight recent advancements transition‐metal‐catalyzed alkenes, underscore utility constructing centers, discuss unsolved challenges future directions field. Key Scientists

Language: Английский

Citations

3
Enantioselective 1,4-Borylamination Enabled by Copper Catalysis DOI
Bo Su, Yu‐Jie Zhu

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

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

Language: Английский

Citations

0