Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis DOI

Minhao Tang,

Z. Yang,

Aijun Han

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 10, 2024

Different from the reported work focusing on construction of single P- or C-stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo- and enantioselective reaction allenes, conjugated enynes 1,3-dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary C- P-stereocenter are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3-enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four P-containing stereoisomers. present protocol features use only 3-minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

Asymmetric Csp3–Csp3 Bond Formation via Ni-Catalyzed Regio- and Enantioselective Hydroalkylation of Linear 1,3-Diene through Carbonyl Umpolung DOI
Ruofei Cheng,

Kangbao Zhong,

Xue‐Qiang Chu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17310 - 17320

Published: Nov. 11, 2024

Asymmetric Csp3–Csp3 bond formation has been a grand pursuit in synthetic chemistry. The regioselective and enantioselective hydroalkylation of 1,3-diene emerged as an appealing approach for constructing chiral allylic bonds. However, this method is presently confined to the use stabilized Csp3 nucleophilic substrates. Herein, we present nickel-catalyzed asymmetric 1,3-dienes with simple unstabilized alkyl carbanion enabled by naturally abundant carbonyls' umpolung under mild reaction conditions. A range alkylated compounds were generated good high yields (up 96%), enantiomeric ratio (er) up 98:2 form bond. protocol applicable heterocycles, polyenes, unsaturated hydrazones well late-stage functionalization various complex pharmaceuticals. Density functional theory calculations elucidated mechanism enantioselectivity reaction. An enantiocontrol model also proposed, emphasizing crucial role NHC ligand facilitating reaction, revealed two-layer two-dimensional (2D) contour maps.

Language: Английский

Citations

1
Recent Advances in Nickel-Catalyzed Asymmetric Hydrofunctionalization of 1,3-Dienes DOI
Jiao Long,

Baixue Liu,

Shuangshuang Zhang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(11), P. 3309 - 3309

Published: Jan. 1, 2024

Language: Английский

Citations

1
Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis DOI

Minhao Tang,

Zhen‐Yu Yang, Aijun Han

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 10, 2024

Abstract Different from the reported work focusing on construction of single P ‐ or C ‐stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo‐ and enantioselective reaction allenes, conjugated enynes 1,3‐dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3‐enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four ‐containing stereoisomers. present protocol features use only 3‐minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

Citations

1
Stereodivergent 1,5-Conjugate Addition with Iminoesters via Pd/Cu Dual Catalysis DOI
Zhi‐Tao He, Zijiang Yang

Synthesis, Journal Year: 2023, Volume and Issue: 56(22), P. 3412 - 3420

Published: Dec. 15, 2023

Abstract The first stereodivergent umpolung 1,5-conjugate addition reaction via synergistic Pd/Cu catalysts is reported. By dictating the absolute configuration of each chiral ligand ligated to corresponding metals, all four stereoisomers products are easily achieved. A series amino acid moieties introduced γ-position conjugated esters in high yields with excellent diastereoselectivities and enantioselectivities. downstream transformations highlight synthetic value method.

Language: Английский

Citations

2
Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis DOI

Xian‐Wang Zeng,

Jia‐Ni Lin,

Wei Shu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(23)

Published: April 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Language: Английский

Citations

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

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: Aug. 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.

Language: Английский

Citations

0
Palladium-catalyzed remote internal C(sp3)−H bond chlorination of alkenes DOI Creative Commons

Yao-Xin Wang,

Zhen Wang, Xiao‐Hui Yang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Dec. 5, 2024

Language: Английский

Citations

0
Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis DOI

Minhao Tang,

Z. Yang,

Aijun Han

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 10, 2024

Different from the reported work focusing on construction of single P- or C-stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo- and enantioselective reaction allenes, conjugated enynes 1,3-dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary C- P-stereocenter are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3-enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four P-containing stereoisomers. present protocol features use only 3-minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

Citations

0