Stereospecific 3‐Aza‐Cope Rearrangement Interrupted Asymmetric Allylic Substitution‐Isomerization DOI Open Access

H.D. Zhuang,

Jun Gu,

Zhiwen Ye

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract Transition‐metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well‐established. However, the arylation of acyclic internal alkenes aryl remains challenging underdeveloped. Herein we report a stereospecific 3‐aza‐Cope rearrangement interrupted substitution‐isomerization ( Int‐AASI ) that enables arylation. By means this stepwise strategy, both enantioenriched products axially chiral could be readily obtained in high enantioselectivities. Experimental studies support mechanism involving cascade amination, alkene isomerization. Density functional theory detailed reasons achieving chemoselectivity, regioselectivity, stereoselectivity stereospecificity, respectively.

Language: Английский

Palladium-Catalyzed Enantioselective Stereodivergent Desymmetrization of Cyclic 1,4-Allyldiboronates DOI
Hao Liang, Lorenzo D. Battistoni,

Sergei Tcyrulnikov

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

In the presence of a chiral palladium-based catalyst, 1,4-diboryl-2-alkenes undergo enantioselective cross-coupling that results in desymmetrization substrate structure. Depending on reaction conditions and choice ligand, can occur with cis or trans selectivity, allowing construction an array different substituted carbocycles enantiomerically enriched fashion.

Language: Английский

Citations

0
Lewis Base-Catalyzed Interhalogenation of Terminal Allenes: Selective Strategy for Accessing Vicinal Vinylic, Allylic Heterodihalides DOI

Alexandra E. Lubaev,

Favour Eze,

Manjula D. Rathnayake

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

Though precedent remains limited, the selective interhalogenation of allenes offers a valuable synthetic strategy to access products where each halide exhibits orthogonal reactivity. Here, we describe Lewis base-catalyzed approach for dihalogenation (bromochlorination, iodochlorination, iodobromination, and dibromination) terminal allenes. By employing just 1 mol % triphenylphosphine oxide or hexamethylphosphoramide activate thionyl halides in presence electrophilic halogenation reagents, achieve conversion monosubstituted vicinal allylic, vinylic dihalides with up 93% yield >20:1 regioisomeric ratio, favoring branched dihalogenated product. A range functional groups is tolerated, including nitrile, ester, phosphate, sulfonamide, silyl groups, reaction proved be scalable. The utility various dihalide was investigated substitution cross-coupling chemistry, highlighting distinct reactivity among different classes.

Language: Английский

Citations

0
Ligand-enabled override of the memory effect in Rh-catalyzed asymmetric Suzuki reactions DOI Creative Commons
Ke Liu, David Egea‐Arrebola, Ruchuta Ardkhean

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102550 - 102550

Published: April 1, 2025

Language: Английский

Citations

0
Copper-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation with 1,1-Diborylalkanes DOI
Minjae Kim, G.N. Kim, Doyoon Kim

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

We report a copper-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of allyl bromides using 1,1-diborylalkanes as prochiral nucleophiles. This methodology employs copper(I) bromide catalyst, an (R)-BINOL-derived phosphoramidite ligand, lithium benzoate crucial additive. The reaction affords enantioenriched homoallylic boronic esters possessing vicinal stereocenters in good yields high diastereo- enantioselectivity. developed method demonstrates broad substrate scope with respect to wide range bromides. Mechanistic studies, including deuterium-labeling experiments DFT calculations, provide insights into the pathway origin stereoselectivity. synthetic utility this is showcased through various transformations obtained valuable chiral building blocks.

Language: Английский

Citations

1
Desymmetrization of Inert meso-Diethers through Copper-Catalyzed Asymmetric Allylic Alkylation with Grignard Reagents DOI
Jun Li, Yu Wang, Yan Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5844 - 5849

Published: July 1, 2024

We have developed a highly regio-, diastereo-, and enantioselective Cu-catalyzed desymmetrization of inert

Language: Английский

Citations

0
Stereospecific 3‐Aza‐Cope Rearrangement Interrupted Asymmetric Allylic Substitution‐Isomerization DOI Open Access

Hongfeng Zhuang,

Jun Gu,

Zhiwen Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Transition-metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well-established. However, the arylation of acyclic internal alkenes aryl remains challenging underdeveloped. Herein we report a stereospecific 3-aza-Cope rearrangement interrupted substitution-isomerization (Int-AASI) that enables arylation. By means this stepwise strategy, both enantioenriched products axially chiral could be readily obtained in high enantioselectivities. Experimental studies support mechanism involving cascade amination, alkene isomerization. Density functional theory detailed reasons achieving chemoselectivity, regioselectivity, stereoselectivity stereospecificity, respectively.

Language: Английский

Citations

0
Stereospecific 3‐Aza‐Cope Rearrangement Interrupted Asymmetric Allylic Substitution‐Isomerization DOI Open Access

H.D. Zhuang,

Jun Gu,

Zhiwen Ye

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract Transition‐metal catalyzed asymmetric allylic substitution with alkyl and heteroaryl carbon nucleophiles has been well‐established. However, the arylation of acyclic internal alkenes aryl remains challenging underdeveloped. Herein we report a stereospecific 3‐aza‐Cope rearrangement interrupted substitution‐isomerization ( Int‐AASI ) that enables arylation. By means this stepwise strategy, both enantioenriched products axially chiral could be readily obtained in high enantioselectivities. Experimental studies support mechanism involving cascade amination, alkene isomerization. Density functional theory detailed reasons achieving chemoselectivity, regioselectivity, stereoselectivity stereospecificity, respectively.

Language: Английский

Citations

0