Ligand-enabled Ni-catalyzed hydroarylation and hydroalkenylation of internal alkenes with organoborons DOI Creative Commons
Daoming Wang,

Li‐Qin She,

Yichen Wu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 12, 2022

The transition metal-catalyzed hydrofunctionalization of alkenes offers an efficient solution for the rapid construction complex functional molecules, and significant progress has been made during last decades. However, internal remains a challenge due to low reactivity difficulties controlling regioselectivity. Here, we report hydroarylation hydroalkenylation lacking directing group with aryl alkenyl boronic acids in presence nickel catalyst, featuring broad substrate scope wide tolerance under redox-neutral conditions. key achieving this reaction is identification bulky 1-adamantyl β-diketone ligand, which capable overcoming 1,2-disubstituted alkenes. Preliminary mechanistic studies unveiled that undergoes Ar-Ni(II)-H initiated process, generated by oxidative addition alcoholic solvent Ni(0) species sequential transmetalation. In addition, proves be turnover-limiting step.

Language: Английский

Synergistic Pd/Amine-Catalyzed Stereodivergent Hydroalkylation of 1,3-Dienes with Aldehydes: Reaction Development, Mechanism, and Stereochemical Origins DOI
Hongfa Wang, Ruiyuan Zhang, Qinglong Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(29), P. 10948 - 10962

Published: July 15, 2021

Metal-hydride-catalyzed hydroalkylation of 1,3-dienes with enolizable carbonyl compounds is an atom- and step-economical method for preparing chiral molecules allylic stereocenters. Although high diastereo- enantioselectivities have been achieved many coupling partners, aldehydes not yet used this purpose because they are less stable than other under basic conditions the potential to rapidly epimerize at α-position. Moreover, stereodivergent reactions access complementary diastereomers vicinal stereocenters challenging. Herein, we describe a synergistic palladium/amine catalyst system that allowed us achieve first aldehydes. By choosing appropriate combination palladium amine catalysts, could obtain either syn or anti products, therefore provides highly enantioselective α,β-vicinal Density functional theory calculations revealed mechanism involving PdH formation migratory insertion into alkene, followed by C–C bond formation. The origin stereoselectivities was investigated means distortion/interaction analysis.

Language: Английский

Citations

120
NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines DOI Creative Commons
Yuli He,

Huayue Song,

Jian Chen

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 27, 2021

Enantiomerically pure chiral amines and related amide derivatives are privilege motifs in many pharmacologically active molecules. In comparison to the well-established hydroamination, transition metal-catalysed asymmetric hydrofunctionalization of enamines provides a complementary approach for their construction. Here we report NiH-catalysed enantio- regioselective reductive hydroarylation N-acyl enamines, allowing practical access broad range structurally diverse, enantioenriched benzylamines under mild, operationally simple reaction conditions.

Language: Английский

Citations

113
Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions DOI
Amanda M. Canfield, Dasha Rodina, Shauna M. Paradine

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 4, 2024

Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.

Language: Английский

Citations

22
Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides DOI
Yuli He, Chuang Liu, Lei Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(48), P. 21530 - 21534

Published: Aug. 28, 2020

Abstract A highly enantio‐ and regioselective hydroarylation process of vinylarenes with aryl halides has been developed using a NiH catalyst new chiral bis imidazoline ligand. broad range structurally diverse, enantioenriched 1,1‐diarylalkanes, structure found in number biologically active molecules, have obtained excellent yields enantioselectivities under extremely mild conditions.

Language: Английский

Citations

130
Palladium-Catalyzed Regio- and Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity DOI
Qinglong Zhang,

Dongfang Dong,

Weiwei Zi

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15860 - 15869

Published: Aug. 19, 2020

Chiral sulfones are important structural motifs in organic synthesis because of their widespread use pharmaceutical chemistry. In particular, chiral allylic have drawn particular interest synthetic utility. However, enantioselective 1,3-disubstituted unsymmetrical remains a challenge. this article, we report protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- and hydrosulfonylation 1,3-dienes with sulfinic acids, which provides atom- step-economical access to sulfones. The reaction occurs under mild conditions has broad substrate scope. Combined experimental computational studies suggest that the is initiated by ligand-to-ligand hydrogen transfer followed C–S bond reductive elimination via six-membered transition state. Steric repulsion between olefinic C–H tert-butyl group (R)-DTBM-Segphos was found be key factor enantiocontrol.

Language: Английский

Citations

122
Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes DOI
Jian Chen, Shaolin Zhu

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14089 - 14096

Published: Aug. 26, 2021

A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation carbonylation from readily available starting materials has been developed. This modular hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range unactivated alkenes to produce wide variety unsymmetrical dialkyl ketones bearing functionalized α-stereocenter, including enantioenriched chiral α-aryl α-amino ketones. It uses bisoxazoline as ligand, silane reductant, chloroformate safe CO source, racemic secondary benzyl chloride or an N-hydroxyphthalimide (NHP) ester protected acid alkylation reagent. The benign nature this process renders method suitable for late-stage functionalization complex molecules.

Language: Английский

Citations

99
Nickel‐Catalyzed, Regio‐ and Enantioselective Benzylic Alkenylation of Olefins with Alkenyl Bromide DOI

Jiandong Liu,

Hegui Gong, Shaolin Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(8), P. 4060 - 4064

Published: Nov. 10, 2020

Abstract A NiH‐catalyzed migratory hydroalkenylation reaction of olefins with alkenyl bromides has been developed, affording benzylic alkenylation products high yields and excellent chemoselectivity. The mild conditions the preclude olefinic from undergoing further isomerization or subsequent alkenylation. Catalytic enantioselective styrenes was achieved by using a chiral bisoxazoline ligand.

Language: Английский

Citations

91
Enantioselective NiH‐Catalyzed Reductive Hydrofunctionalization of Alkenes DOI
Yuli He, Jian Chen, Xiaoli Jiang

et al.

Chinese Journal of Chemistry, Journal Year: 2021, Volume and Issue: 40(5), P. 651 - 661

Published: Dec. 3, 2021

Comprehensive Summary Enantioselective NiH‐catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years. Using simple chiral ligands, a wide array functionalized and electrophiles can undergo diverse transformations to afford hydrofunctionalized products, regio‐ enantioselectively. These processes avoid the prior preparation organometallic reagents, construct stereogenic center at carbon originating either from olefin or electrophile. This review discusses background, major progress mechanistic investigations this reaction.

Language: Английский

Citations

86
Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH‐Catalyzed Hydroamination DOI

Lingpu Meng,

Jingjie Yang,

Mei Duan

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23584 - 23589

Published: Aug. 27, 2021

Regio- and enantioselective hydroarylamination, hydroalkylamination hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range enantioenriched benzylic arylamines, alkylamines amides can be easily accessed nitroarenes, hydroxylamines dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.

Language: Английский

Citations

73
Stereodivergent Synthesis of BothZ- andE-Alkenes by Photoinduced, Ni-Catalyzed Enantioselective C(sp3)–H Alkenylation DOI
Jitao Xu, Zhilong Li,

Yumin Xu

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13567 - 13574

Published: Oct. 25, 2021

The enantio- and stereoselective synthesis of stereodefined alkenes, especially the functionalized Z-isomer with an allylic stereogenic center, remains a great challenge. We herein report enantioselective benzylic C(sp3)–H alkenylation simple alkylarenes vinyl bromides via photoinduced nickel catalysis, which allows for stereodivergent both enantioenriched Z- E-alkenes bearing aryl-substituted, tertiary centers. Interestingly, tunable Z/E-selectivity is achieved by energy transfer catalysis judicious choice photocatalyst counteranion. This versatile strategy features starting materials, mild reaction conditions, broad substrate scope, divergent E-selectivity, high enantioselectivities. Moreover, formal asymmetric alkylation can also be one-pot alkenylation/reduction sequence, providing complementary to address notoriously challenging stereochemical control in C(sp3)–C(sp3) bond construction.

Language: Английский

Citations

67