Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes DOI
Xiang Lyu, Jianbo Zhang, Dongwook Kim

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(15), P. 5867 - 5877

Published: April 9, 2021

The formal hydroamination/hydroamidation utilizing metal hydride is an appealing synthetic tool for the construction of valuable nitrogen-containing compounds from unsaturated hydrocarbons. While significant advances have been made functionalizations alkenes in this realm, direct hydroamidation alkynes remains rather limited due to high feasibility key metal-alkenyl intermediate choose other reaction pathways. Herein, we report a NiH-catalyzed strategy with dioxazolones, which allows convenient access synthetically useful secondary enamides (E)-anti-Markovnikov or Markovnikov selectivity. viable both terminal and internal also tolerant range subtle functional groups. With H2O found as essential component catalyst turnovers, involvement inner-sphere nitrenoid transfer proposed that outcompetes undesired semireduction process, thus representing first example show competence Ni catalysis metal-nitrenoid formation dioxazolones.

Language: Английский

Nickel-Catalyzed Dicarbofunctionalization of Alkenes DOI

Xiaoxu Qi,

Tianning Diao

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(15), P. 8542 - 8556

Published: July 2, 2020

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available with electrophiles and/or nucleophiles. Nickel complexes serve effective catalysts owing to their tendency undergo facile oxidative addition and slow β-hydride elimination, capability access both two-electron radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, stereoselectivities tethering one the partners substrate. Three-component reactions, however, often incorporate directing groups control selectivity. Only a few examples directing-group-free difunctionalizations unactivated been reported. Therefore, great opportunities exist development three-component difunctionalization broad substrate scopes tunable stereoselectivities.

Language: Английский

Citations

382
Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles DOI
Weichao Xue, Xiao Jia, Xuan Wang

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(6), P. 4162 - 4184

Published: Jan. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Language: Английский

Citations

173
Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles DOI

Shi-Jiang He,

Jia‐Wang Wang, Yan Li

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 142(1), P. 214 - 221

Published: Dec. 15, 2019

Substantial advances in enantioconvergent C(sp3)–C(sp3) bond formation reactions have been made recent years through the use of transition-metal-catalyzed cross-coupling racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for asymmetric construction alkyl–alkyl bonds adjacent to heteroatoms, namely, nickel-catalyzed reductive hydroalkylation olefins α-heteroatom phosphorus or sulfur electrophiles. Including readily available olefins, this reaction has considerable advantages, such as mild conditions, broad substrate scope, and good functional group compatibility, making it desirable alternative traditional electrophile–nucleophile reactions.

Language: Английский

Citations

168
Enantioselective C(sp3)–C(sp3) cross-coupling of non-activated alkyl electrophiles via nickel hydride catalysis DOI
Srikrishna Bera, Runze Mao, Xile Hu

et al.

Nature Chemistry, Journal Year: 2020, Volume and Issue: 13(3), P. 270 - 277

Published: Dec. 30, 2020

Language: Английский

Citations

167
Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes DOI
Xiaoxu Wang, Xi Lu, Yan Li

et al.

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(11), P. 1586 - 1600

Published: Sept. 28, 2020

Language: Английский

Citations

152
NiH-Catalyzed Functionalization of Remote and Proximal Olefins: New Reactions and Innovative Strategies DOI
You Wang, Yuli He, Shaolin Zhu

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(23), P. 3519 - 3536

Published: Nov. 9, 2022

Transition metal hydride catalyzed functionalization of remote and proximal olefins has many advantages over conventional cross-coupling reactions. It avoids the separate, prior generation stoichiometric amounts organometallic reagents use preformed reagents, which are sometimes hard to access may compromise functional group compatibility. The migratory insertion complexes generated in situ into readily available alkene starting materials, hydrometalation process, provides an attractive straightforward route alkyl intermediates, can undergo a variety sequential In particular, with synergistic combination chain-walking chemistry nickel, NiH-catalyzed undergone particularly intense development past few years. This Account aims chronicle progress made this arena terms activation modes, diverse functionalizations, chemo-, regio-, enantioselectivity.We first provide brief introduction general reaction mechanisms. Taking hydroarylation as example, four oxidation states Ni have allowed us develop two different strategies form final product: Ni(I)-H/X-Ni(II)-H platform that relies on reductants Ni(I/II/III) cycle redox-neutral or FG-Ni(II)-H reacts substrate forms products via Ni(0/II) pathway. We also demonstrate functionalization, including C-C bond-forming reactions more challenging C-N/C-S could be realized. Moreover, employment appropriate chiral ligands successfully realize corresponding asymmetric hydrofunctionalization olefins, hydroalkylation, hydroarylation, hydroalkenylation, hydroalkynylation, hydroamination. Interestingly, enantio-determining step enantioselective hydronickelation, selective oxidative addition, reductive elimination. To hydrofunctionalization, we developed ligand relay catalytic strategy simple ligands, for second coupling. novel design single, possibly structurally complex promote both steps success multicomponent convenient approach gain molecules. Finally, halides used olefin precursors cross-electrophile coupling Applications these discussed. hope will inspire future field overcome key challenges, conceptually new strategies, high-performance systems enhanced reactivity selectivity, cutting-edge catalyst design, further mechanistic studies.

Language: Английский

Citations

143
Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes DOI
Zhikun Zhang, Srikrishna Bera, Chao Fan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7015 - 7029

Published: April 12, 2022

Compounds rich in sp3-hybridized carbons are desirable drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable as pro-nucleophiles, reactions can have broad scope high functional group tolerance. However, this methodology still an early stage development, the first examples were reported only 2016. Herein, we summarize progress emerging field, with emphasis on enantioselective reactions. We highlight major developments, critically discuss wide range possible mechanisms, offer our perspective state challenges field. hope Perspective will stimulate future works area, making widely applicable organic synthesis.

Language: Английский

Citations

128
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
Native Amides as Enabling Vehicles for Forging sp3–sp3 Architectures via Interrupted Deaminative Ni-Catalyzed Chain-Walking DOI Creative Commons
Jesus Rodrigalvarez, Hao Wang, Rubén Martı́n

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3869 - 3874

Published: Feb. 8, 2023

Herein, we disclose an interrupted deaminative Ni-catalyzed chain-walking strategy that forges sp3-sp3 architectures at remote, yet previously unfunctionalized, methylene sp3 C-H sites enabled by the presence of native amides. This protocol is characterized its mild conditions and wide scope, including challenging substrate combinations. Site-selectivity can be dictated a judicious choice ligand, thus offering opportunity to enable bond formations are otherwise inaccessible in conventional events.

Language: Английский

Citations

57
Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking DOI Creative Commons
Jacob Davies, Julien R. Lyonnet,

Bjørn Carvalho

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1753 - 1759

Published: Jan. 9, 2024

Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by merger photoredox and nickel catalysis, a previously inaccessible endeavor in arena. Site-selectivity is dictated kinetically controlled insertion CO2 at initial C(sp3)–Br site rapid formation Ni(I)–alkyl species, thus avoiding undesired β-hydride elimination chain-walking processes. Preliminary mechanistic experiments reveal subtleties stereoelectronic effects for guiding reactivity site-selectivity.

Language: Английский

Citations

16