Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes DOI
Shuailong Li, Dequan Zhang, Runtong Zhang

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 134(33)

Опубликована: Июнь 18, 2022

Abstract The first rhodium‐catalyzed highly chemo‐, regio‐ and enantioselective hydroformylation of cyclopropyl‐functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named ( R , S )‐DTBM‐Yanphos, can convert a series readily available into high‐value aldehydes with high selectivities (81–98 % ee ). Gram‐scale reactions (TON up 1500) follow‐up transformations corresponding alcohol, acid, esters nitrile are also presented. Finally, possible mechanism involving ring‐open‐hydroformylation pathways proposed based on control deuteroformylation reactions.

Язык: Английский

Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species DOI
Wu Yang, Lin Liu, Jiandong Guo

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Июнь 2, 2022

Catalytic enantioselective hydroxylation of prochiral dihydrosilanes with water is expected to be a highly efficient way access Si-chiral silanols, yet has remained unknown up date. Herein, we describe strategy for realizing this reaction: using an alkyl bromide as single-electron transfer (SET) oxidant invoking CuII species and chiral multidentate anionic N,N,P-ligands effective enantiocontrol. The reaction readily provides broad range silanols high enantioselectivity excellent functional group compatibility. In addition, manifest the synthetic potential by establishing two schemes transforming obtained products into compounds structural diversity. Our preliminary mechanistic studies support mechanism involving SET recruiting active catalyst its subsequent σ-metathesis dihydrosilanes.

Язык: Английский

Процитировано

36

Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes DOI
Shuailong Li, Dequan Zhang, Runtong Zhang

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 18, 2022

The first rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)-DTBM-Yanphos, can convert a series readily available into high-value aldehydes with high selectivities (81-98 % ee). Gram-scale reactions (TON up 1500) follow-up transformations corresponding alcohol, acid, esters nitrile are also presented. Finally, possible mechanism involving ring-open-hydroformylation pathways proposed based on control deuteroformylation reactions.

Язык: Английский

Процитировано

19

Chiral phosphoric acid-catalyzed enantioselective phosphinylation of 3,4-dihydroisoquinolines with diarylphosphine oxides DOI Creative Commons
Yongbiao Guo, Ning Li, Junchen Li

и другие.

Communications Chemistry, Год журнала: 2023, Номер 6(1)

Опубликована: Фев. 9, 2023

Chiral phosphorous-containing compounds are playing a more and significant role in several different research fields. Here, we show chiral phosphoric acid-catalyzed enantioselective phosphinylation of 3,4-dihydroisoquinolines with diarylphosphine oxides for the efficient practical construction family α-amino diverse range functional groups. The phosphine products suitable transforming to kinds (thio)ureas, which might be employed as ligands or catalysts potential applications asymmetric catalysis. Control NMR tracking experiments that reaction proceeds via tert-butyl 1-(tert-butoxy)-3,4-dihydroiso-quinoline-2(1H)-carboxylate intermediate, followed by C-P bond formation. Furthermore, computational studies elucidated hydrogen bonding strength between phosphonate isoquinolinium determines stereoselectivity reaction.

Язык: Английский

Процитировано

10

Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles DOI
Huan Guo,

Ningning Sun,

Juan Guo

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(16)

Опубликована: Фев. 15, 2023

Herein, we disclose the highly enantioselective oxidative cross-coupling of 3-hydroxyindole esters with various nucleophilic partners as catalyzed by copper efflux oxidase. The biocatalytic transformation delivers functionalized 2,2-disubstituted indolin-3-ones excellent optical purity (90-99 % ee), which exhibited anticancer activity against MCF-7 cell lines, shown preliminary biological evaluation. Mechanistic studies and molecular docking results suggest formation a phenoxyl radical enantiocontrol facilitated suited enzyme chiral pocket. This study is significant regard to expanding catalytic repertoire natural multicopper oxidases well enlarging synthetic toolbox for sustainable asymmetric coupling.

Язык: Английский

Процитировано

8

Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species DOI
Wu Yang, Lin Liu, Jiandong Guo

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 134(32)

Опубликована: Июнь 2, 2022

Abstract Catalytic enantioselective hydroxylation of prochiral dihydrosilanes with water is expected to be a highly efficient way access Si‐chiral silanols, yet has remained unknown up date. Herein, we describe strategy for realizing this reaction: using an alkyl bromide as single‐electron transfer (SET) oxidant invoking Cu II species and chiral multidentate anionic N,N,P‐ligands effective enantiocontrol. The reaction readily provides broad range silanols high enantioselectivity excellent functional group compatibility. In addition, manifest the synthetic potential by establishing two schemes transforming obtained products into compounds structural diversity. Our preliminary mechanistic studies support mechanism involving SET recruiting active catalyst its subsequent σ ‐metathesis dihydrosilanes.

Язык: Английский

Процитировано

12

Enantio‐ and Regioselective Copper‐Catalyzed 1,2‐Dearomatization of Pyridines DOI Creative Commons
Mukesh Pappoppula,

Kathryn L. Olsen,

Devin R. Ketelboeter

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 11, 2023

A copper-catalyzed dearomative alkynylation of pyridines is reported with excellent regio- and enantioselectivities. The synthetically valuable enantioenriched 2-alkynyl-1,2-dihydropyridine products afforded are generated from the readily available feedstock, pyridine, commercially terminal alkynes. three-component reaction between a alkyne, methyl chloroformate employs copper chloride StackPhos, chiral biaryl P,N- ligand, as catalytic system. Under mild conditions, desired 1,2-addition delivered in up to 99 % yield regioselectivity ratios 25 : 1 enantioselectivities values ee. Activated non-activated alkynes containing wide range functional groups well tolerated. Even acetylene gas mono-alkynylated high Application methodology an efficient enantioselective synthesis piperidine indolizidine, coniceine, reported.

Язык: Английский

Процитировано

6

Enantioselective phosphonation of isoquinolines via chiral phosphoric acid-catalyzed dearomatization DOI
Zhenhua Gao, Yongbiao Guo

Chemical Communications, Год журнала: 2022, Номер 58(67), С. 9393 - 9396

Опубликована: Янв. 1, 2022

An efficient and enantioselective phosphonation of isoquinolines via chiral phosphoric acid-catalyzed dearomatization has been developed.

Язык: Английский

Процитировано

10

Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles DOI
Huan Guo,

Ningning Sun,

Juan Guo

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(16)

Опубликована: Фев. 15, 2023

Abstract Herein, we disclose the highly enantioselective oxidative cross‐coupling of 3‐hydroxyindole esters with various nucleophilic partners as catalyzed by copper efflux oxidase. The biocatalytic transformation delivers functionalized 2,2‐disubstituted indolin‐3‐ones excellent optical purity (90–99 % ee ), which exhibited anticancer activity against MCF‐7 cell lines, shown preliminary biological evaluation. Mechanistic studies and molecular docking results suggest formation a phenoxyl radical enantiocontrol facilitated suited enzyme chiral pocket. This study is significant regard to expanding catalytic repertoire natural multicopper oxidases well enlarging synthetic toolbox for sustainable asymmetric coupling.

Язык: Английский

Процитировано

0

Enantio‐ and Regioselective Copper‐Catalyzed 1,2‐Dearomatization of Pyridines DOI Open Access
Mukesh Pappoppula,

Kathryn L. Olsen,

Devin R. Ketelboeter

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(48)

Опубликована: Окт. 11, 2023

Abstract A copper‐catalyzed dearomative alkynylation of pyridines is reported with excellent regio‐ and enantioselectivities. The synthetically valuable enantioenriched 2‐alkynyl‐1,2‐dihydropyridine products afforded are generated from the readily available feedstock, pyridine, commercially terminal alkynes. three‐component reaction between a alkyne, methyl chloroformate employs copper chloride StackPhos, chiral biaryl P , N‐ ligand, as catalytic system. Under mild conditions, desired 1,2‐addition delivered in up to 99 % yield regioselectivity ratios 25 : 1 enantioselectivities values ee. Activated non‐activated alkynes containing wide range functional groups well tolerated. Even acetylene gas mono‐alkynylated high Application methodology an efficient enantioselective synthesis piperidine indolizidine, coniceine, reported.

Язык: Английский

Процитировано

0

Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes DOI
Shuailong Li, Dequan Zhang, Runtong Zhang

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 134(33)

Опубликована: Июнь 18, 2022

Abstract The first rhodium‐catalyzed highly chemo‐, regio‐ and enantioselective hydroformylation of cyclopropyl‐functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named ( R , S )‐DTBM‐Yanphos, can convert a series readily available into high‐value aldehydes with high selectivities (81–98 % ee ). Gram‐scale reactions (TON up 1500) follow‐up transformations corresponding alcohol, acid, esters nitrile are also presented. Finally, possible mechanism involving ring‐open‐hydroformylation pathways proposed based on control deuteroformylation reactions.

Язык: Английский

Процитировано

0