Stereodivergent Construction of Csp3−Csp3Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis DOI

Jingqiang Han,

Rixin Liu,

Zitong Lin

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 135(2)

Опубликована: Ноя. 16, 2022

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation Csp 3 −Csp bonds bearing vicinal stereocenters. Despite many successes that have been achieved in this field, coupling reactions involving stabilized nucleophiles remain challenging because competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system enables diastereodivergent 1,3‐dienes with nucleophile oxindoles. Both syn and anti products, quaternary tertiary stereocenters, could be selectively produced good yields high enantio‐ diastereoselectivities. Non‐covalent activation via chiral ion pair biphasic is crucial success factor achieving diastereodivergence.

Язык: Английский

Stereodivergent Construction of Csp3−Csp3Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis DOI

Jingqiang Han,

Rixin Liu,

Zitong Lin

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(2)

Опубликована: Ноя. 16, 2022

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation Csp 3 −Csp bonds bearing vicinal stereocenters. Despite many successes that have been achieved in this field, coupling reactions involving stabilized nucleophiles remain challenging because competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system enables diastereodivergent 1,3‐dienes with nucleophile oxindoles. Both syn and anti products, quaternary tertiary stereocenters, could be selectively produced good yields high enantio‐ diastereoselectivities. Non‐covalent activation via chiral ion pair biphasic is crucial success factor achieving diastereodivergence.

Язык: Английский

Процитировано

40
Synergistic Palladium/Copper‐Catalyzed 1,4‐Difunctionalization of 1,3‐Dienes for Stereodivergent Construction of 1,5‐Nonadjacent Stereocenters DOI
Hongfa Wang, Ruiyuan Zhang, Weiwei Zi

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 21, 2024

Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.

Язык: Английский

Процитировано

14
Enantioselective Three‐Component Photochemical 1,4‐Bisalkylation of 1,3‐Butadiene with Pd/Cu Catalysis DOI
Huimin Yu, Qinglong Zhang, Weiwei Zi

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Июнь 27, 2022

Catalysis by excited-state palladium has emerged as an active area of research, but controlling the enantioselectivity remains a challenge. Herein, we report use synergistic Pd/Cu catalysis to accomplish first three-component photochemical 1,4-bisalkylation reactions 1,3-butadiene. Consequently, α-amino acid esters bearing quaternary stereocenters were expeditiously synthesized from three simple starting materials: alkyl bromide, butadiene, and aldimine ester. Experimental computational investigation reaction mechanism confirmed radical pathway involving species. The stereochemistry is mainly controlled chiral Cu catalyst.

Язык: Английский

Процитировано

34
Iridium‐Catalyzed Chemo‐, Diastereo‐, and Enantioselective Allyl‐Allyl Coupling: Accessing All Four Stereoisomers of (E)‐1‐Boryl‐Substituted 1,5‐Dienes by Chirality Pairing DOI

Yongsuk Jung,

Seok Yeol Yoo,

Yonghoon Jin

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(13)

Опубликована: Янв. 31, 2023

Here, we report a highly chemo-, diastereo-, and enantioselective allyl-allyl coupling between branched allyl alcohols α-silyl-substituted allylboronate esters, catalyzed by chiral iridium complex. The esters can be chemoselectively coupled with electrophiles, affording diverse set of enantioenriched (E)-1-boryl-substituted 1,5-dienes in good yields, excellent stereoselectivity. By permuting the catalysts substrates, efficiently selectively obtained all four stereoisomers bearing two consecutive centers. Mechanistic studies via density functional theory calculations revealed origins diastereo- chemoselectivities, indicating pivotal roles steric interaction, β-silicon effect, rapid desilylation process. Additional synthetic modifications for preparing variety compounds containing contiguous centers are also included.

Язык: Английский

Процитировано

19
Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI Open Access
Yufan Li,

Wu-Tao Gui,

Fu Pi

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Авг. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Язык: Английский

Процитировано

3
Stereodivergent dual catalysis in organic synthesis DOI

Hong Sun,

Yue Ma,

Guorong Xiao

и другие.

Trends in Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 1, 2024

Язык: Английский

Процитировано

3
Enantioselective Three‐Component Photochemical 1,4‐Bisalkylation of 1,3‐Butadiene with Pd/Cu Catalysis DOI
Huimin Yu, Qinglong Zhang, Weiwei Zi

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 134(40)

Опубликована: Июнь 27, 2022

Abstract Catalysis by excited‐state palladium has emerged as an active area of research, but controlling the enantioselectivity remains a challenge. Herein, we report use synergistic Pd/Cu catalysis to accomplish first three‐component photochemical 1,4‐bisalkylation reactions 1,3‐butadiene. Consequently, α‐amino acid esters bearing quaternary stereocenters were expeditiously synthesized from three simple starting materials: alkyl bromide, butadiene, and aldimine ester. Experimental computational investigation reaction mechanism confirmed radical pathway involving species. The stereochemistry is mainly controlled chiral Cu catalyst.

Язык: Английский

Процитировано

3
Iridium‐Catalyzed Chemo‐, Diastereo‐, and Enantioselective Allyl‐Allyl Coupling: Accessing All Four Stereoisomers of (E)‐1‐Boryl‐Substituted 1,5‐Dienes by Chirality Pairing DOI

Yongsuk Jung,

Seok Yeol Yoo,

Yonghoon Jin

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(13)

Опубликована: Янв. 31, 2023

Abstract Here, we report a highly chemo‐, diastereo‐, and enantioselective allyl‐allyl coupling between branched allyl alcohols α‐silyl‐substituted allylboronate esters, catalyzed by chiral iridium complex. The esters can be chemoselectively coupled with electrophiles, affording diverse set of enantioenriched ( E )‐1‐boryl‐substituted 1,5‐dienes in good yields, excellent stereoselectivity. By permuting the catalysts substrates, efficiently selectively obtained all four stereoisomers bearing two consecutive centers. Mechanistic studies via density functional theory calculations revealed origins diastereo‐ chemoselectivities, indicating pivotal roles steric interaction, β‐silicon effect, rapid desilylation process. Additional synthetic modifications for preparing variety compounds containing contiguous centers are also included.

Язык: Английский

Процитировано

1
Synergistic Palladium/Copper‐Catalyzed 1,4‐Difunctionalization of 1,3‐Dienes for Stereodivergent Construction of 1,5‐Nonadjacent Stereocenters DOI
Hongfa Wang, Ruiyuan Zhang, Weiwei Zi

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(21)

Опубликована: Март 21, 2024

Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.

Язык: Английский

Процитировано

0
Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI
Yufan Li,

Wu-Tao Gui,

Fu Pi

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(44)

Опубликована: Авг. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Язык: Английский

Процитировано

0