From gem‐Dichlorocyclobutenones to Cyclobutenols: Unveiling a Ruthenium‐Catalyzed Allylic Reduction‐Asymmetric Transfer Hydrogenation Cascade DOI
Christophe Meyer,

Olivier Charron,

Marharyta Kosiuha

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract Cyclobutenones constitute an appealing class of substrates in catalytic asymmetric transformations leading to diversely substituted enantioenriched four‐membered carbocycles, which are eliciting a growing interest medicinal chemistry. Whilst several synthetically useful enantioselective conjugate addition reactions have been reported, the reduction carbonyl group simple cyclobutenones remains elusive transformation. Herein, we disclose discovery novel allylic reduction‐asymmetric transfer hydrogenation cascade, catalyzed by Noyori‐Ikariya ruthenium complex, from readily available gem ‐dichlorocyclobutenones, 2‐chlorocyclobutenols with high optical purities, can be engaged postfunctionalization enabling access rings.

Language: Английский

Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones DOI
Xiaolin Li,

Jiang-Lian Deng,

Jian Long

et al.

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

Published: Oct. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Language: Английский

Citations

1
Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones DOI
Xiaolin Li,

Jiang-Lian Deng,

Jian Long

et al.

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

Published: Oct. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Language: Английский

Citations

0
Catalytic Asymmetric Conjugate Addition and Allylic Substitution of Cyclobutenones with Arylzinc Halides DOI
Renming Pan, Ping Lu

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Comprehensive Summary Conjugate addition and allylic substitution are two essential chemical transformations, they could be competitive for substrates with multiple reactive sites. Herein, we report the diversified enantioselective synthesis of cyclobutenes via functionalization cyclobutenones. The conjugate cyclobutenones arylzinc halides provided enantioenriched all‐carbon quaternary centers. On other hand, when gem ‐dichloro groups were employed, a chemo‐ occurred. Further synthetic utility was demonstrated synthesizing versatile cyclobutane derivatives, together ring‐opening expansion products.

Language: Английский

Citations

0
From gem‐Dichlorocyclobutenones to Cyclobutenols: Unveiling a Ruthenium‐Catalyzed Allylic Reduction‐Asymmetric Transfer Hydrogenation Cascade DOI
Christophe Meyer,

Olivier Charron,

Marharyta Kosiuha

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract Cyclobutenones constitute an appealing class of substrates in catalytic asymmetric transformations leading to diversely substituted enantioenriched four‐membered carbocycles, which are eliciting a growing interest medicinal chemistry. Whilst several synthetically useful enantioselective conjugate addition reactions have been reported, the reduction carbonyl group simple cyclobutenones remains elusive transformation. Herein, we disclose discovery novel allylic reduction‐asymmetric transfer hydrogenation cascade, catalyzed by Noyori‐Ikariya ruthenium complex, from readily available gem ‐dichlorocyclobutenones, 2‐chlorocyclobutenols with high optical purities, can be engaged postfunctionalization enabling access rings.

Language: Английский

Citations

0