Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Reductive Coupling of 1,3‐Dienes and Aldehydes DOI
Yu Wang,

Danrui Wang,

Shilin Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Сен. 4, 2024

Catalytic regio-, diastereo- and enantioselective reductive coupling of 1,3-dienes aldehydes through regio- oxidative cyclization followed by diastereoselective protonation promoted a chiral phosphine-cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable selective transformation the more substituted alkene in 1,3-dienes, affording broad scope bishomoallylic alcohols without need pre-formation stoichiometric amounts sensitive organometallic reagents up to 98 % yield, >98 : 2 regioselectivity, dr er. Application this method construction axial stereogenicity deuterated stereogenic center provided wide range multifunctional building blocks are otherwise difficult access. DFT calculations revealed origin stereoselectivity as well unique mechanism catalysis.

Язык: Английский

Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes DOI

Chuiyi Lin,

Jiwu Zhang,

Zhao Sun

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 31, 2024

Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for catalysis and general approach that enable rapid construction highly diversified enantioenriched allylic alcohols containing 1,1-, 1,2-disubstituted trisubstituted alkene as well axial stereogenicity in up to 99 % yield : 1 er without the need preformation alkenyl-metal reagents. DFT calculations revealed origin enantioselectivity.

Язык: Английский

Процитировано

9
Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis DOI

Pei Gu,

Linlin Ding,

Xiaowu Fang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(37)

Опубликована: Июнь 25, 2024

Abstract Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for synthesis of alcohols, it suffers drawbacks such as use toxic chromium salts, high amounts metal reductants, poor enantiocontrol. To address these limitations, we present novel approach involving metallaphotoredox‐catalyzed asymmetric NHK production chiral alcohols. This marries (pseudo)halides with aldehydes, leveraging synergistic blend nickel catalyst photocatalyst. innovative technique enables oxidative addition insertion just using nickel, diverging significantly conventional pathway mediated by salts. The adoption this methodology holds immense promise crafting spectrum intricate compounds, particularly those significance pharmaceuticals. Detailed experimental investigations have shed light on metallaphotoredox process, further enhancing our understanding enabling advancements.

Язык: Английский

Процитировано

5
Recent advances of the Grignard-type reactions without involving organohalides DOI

Yu Huang,

Ruizhi Yang, Wenbo Liu

и другие.

Tetrahedron Chem, Год журнала: 2024, Номер 9, С. 100069 - 100069

Опубликована: Фев. 28, 2024

Язык: Английский

Процитировано

0
Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes DOI

Chuiyi Lin,

Jiwu Zhang,

Zhao Sun

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Май 31, 2024

Abstract Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for catalysis and general approach that enable rapid construction highly diversified enantioenriched allylic alcohols containing 1,1‐, 1,2‐disubstituted trisubstituted alkene as well axial stereogenicity in up to 99 % yield : 1 er without the need preformation alkenyl–metal reagents. DFT calculations revealed origin enantioselectivity.

Язык: Английский

Процитировано

0
Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis DOI

Pei Gu,

Linlin Ding,

Xiaowu Fang

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(37)

Опубликована: Июнь 25, 2024

Abstract Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for synthesis of alcohols, it suffers drawbacks such as use toxic chromium salts, high amounts metal reductants, poor enantiocontrol. To address these limitations, we present novel approach involving metallaphotoredox‐catalyzed asymmetric NHK production chiral alcohols. This marries (pseudo)halides with aldehydes, leveraging synergistic blend nickel catalyst photocatalyst. innovative technique enables oxidative addition insertion just using nickel, diverging significantly conventional pathway mediated by salts. The adoption this methodology holds immense promise crafting spectrum intricate compounds, particularly those significance pharmaceuticals. Detailed experimental investigations have shed light on metallaphotoredox process, further enhancing our understanding enabling advancements.

Язык: Английский

Процитировано

0
Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Reductive Coupling of 1,3‐Dienes and Aldehydes DOI
Yu Wang,

Danrui Wang,

Shilin Wang

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 137(1)

Опубликована: Сен. 4, 2024

Abstract Catalytic regio‐, diastereo‐ and enantioselective reductive coupling of 1,3‐dienes aldehydes through regio‐ oxidative cyclization followed by diastereoselective protonation promoted a chiral phosphine‐cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable selective transformation the more substituted alkene in 1,3‐dienes, affording broad scope bishomoallylic alcohols without need pre‐formation stoichiometric amounts sensitive organometallic reagents up to 98 % yield, >98 : 2 regioselectivity, dr er. Application this method construction axial stereogenicity deuterated stereogenic center provided wide range multifunctional building blocks are otherwise difficult access. DFT calculations revealed origin stereoselectivity as well unique mechanism catalysis.

Язык: Английский

Процитировано

0
Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Reductive Coupling of 1,3‐Dienes and Aldehydes DOI
Yu Wang,

Danrui Wang,

Shilin Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Сен. 4, 2024

Catalytic regio-, diastereo- and enantioselective reductive coupling of 1,3-dienes aldehydes through regio- oxidative cyclization followed by diastereoselective protonation promoted a chiral phosphine-cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable selective transformation the more substituted alkene in 1,3-dienes, affording broad scope bishomoallylic alcohols without need pre-formation stoichiometric amounts sensitive organometallic reagents up to 98 % yield, >98 : 2 regioselectivity, dr er. Application this method construction axial stereogenicity deuterated stereogenic center provided wide range multifunctional building blocks are otherwise difficult access. DFT calculations revealed origin stereoselectivity as well unique mechanism catalysis.

Язык: Английский

Процитировано

0