Cobalt‐Catalyzed Regiodivergent Double Hydrosilylation of Arylacetylenes DOI
Zhaoyang Cheng, Minghua Li,

Xu‐Yang Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Nov. 4, 2022

Abstract Double hydrosilylation of alkynes represents a straightforward method to synthesize bis(silane)s, yet it is challenging if α‐substituted vinylsilanes act as the intermediates. Here, cobalt‐catalyzed regiodivergent double arylacetylenes reported for first time involving this challenge, accessing both vicinal and geminal bis(silane)s with exclusive regioselectivity. Various novel containing Si−H bonds can be easily obtained. The gram‐scale reactions could performed smoothly. Preliminarily mechanistic studies demonstrated that were initiated by α‐hydrosilylation alkynes, followed β‐hydrosilylation α‐vinylsilanes deliver or hydride‐catalyzed give ones. Notably, these used synthesis high‐refractive‐index polymers ( n d up 1.83), demonstrating great potential utility in optical materials.

Language: Английский

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules DOI Creative Commons
Sara Kopf, Florian Bourriquen, Wu Li

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 6634 - 6718

Published: Feb. 18, 2022

Organic compounds labeled with hydrogen isotopes play a crucial role in numerous areas, from materials science to medicinal chemistry. Indeed, while the replacement of by deuterium gives rise improved absorption, distribution, metabolism, and excretion (ADME) properties drugs enables preparation internal standards for analytical mass spectrometry, use tritium-labeled is key technique all along drug discovery development pharmaceutical industry. For these reasons, interest new methodologies isotopic enrichment organic molecules extent their applications are equally rising. In this regard, Review intends comprehensively discuss developments area over last years (2017–2021). Notably, besides fundamental isotope exchange (HIE) reactions isotopically analogues common reagents, plethora reductive dehalogenative deuteration techniques other transformations incorporation emerging now part labeling toolkit.

Language: Английский

Citations

379
Recent Advances in Catalytic Hydrosilylations: Developments beyond Traditional Platinum Catalysts DOI
Leandro D. Almeida, Hongli Wang, Kathrin Junge

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(2), P. 550 - 565

Published: July 15, 2020

Hydrosilylation reactions, which allow the addition of Si-H to C=C/C≡C bonds, are typically catalyzed by homogeneous noble metal catalysts (Pt, Rh, Ir, and Ru). Although excellent activity selectivity can be obtained, price, purification, residues these precious problems in silicone industry. Thus, a strong interest more sustainable for economic processes exists. In this respect, recently disclosed hydrosilylations using based on earth-abundant transition metals, example, Fe, Co, Ni, Mn, heterogeneous (supported nanoparticles single-atom sites) noteworthy. This minireview describes recent advances field.

Language: Английский

Citations

248
Cobalt-Catalyzed Sequential Site- and Stereoselective Hydrosilylation of 1,3- and 1,4-Enynes DOI

Wenxin Lu,

Yongmei Zhao,

Fanke Meng

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5233 - 5240

Published: March 17, 2022

Catalytic sequential hydrosilylation of 1,3-enynes and 1,4-enynes promoted by cobalt complexes derived from bisphosphines are presented. Site- stereoselective Si–H addition primary silanes to followed intramolecular diastereo- enantioselective afforded enantioenriched cyclic alkenylsilanes with simultaneous construction a carbon-stereogenic center silicon-stereogenic center. Reactions proceeded through isomerization the alkene moiety site- hydrosilylation. A wide range were in high efficiency selectivity. Functionalization containing stereogenic at silicon delivered variety chiral building blocks that otherwise difficult access.

Language: Английский

Citations

76
Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation** DOI
Jia‐Wang Wang, Deguang Liu, Zhe Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Language: Английский

Citations

66
Well-defined coordination environment breaks the bottleneck of organic synthesis: Single-atom palladium catalyzed hydrosilylation of internal alkynes DOI

Shicheng Ren,

Bochao Ye,

Siying Li

et al.

Nano Research, Journal Year: 2021, Volume and Issue: 15(2), P. 1500 - 1508

Published: Aug. 10, 2021

Language: Английский

Citations

64
Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation DOI
Dongyang Wang,

Yuhang Lai,

Peng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12847 - 12856

Published: Aug. 4, 2021

Metal-catalyzed hydrosilylation of alkynes is an ideal atom-economic method to prepare vinylsilanes that are useful reagents in the organic synthesis and silicone industry. Although great success has been made preparation β-vinylsilanes by metal-catalyzed reactions alkynes, reported for α-vinylsilanes suffer from narrow substrate scope and/or poor selectivity. Herein, we present selective Markovnikov terminal with tertiary silanes using a dicobalt carbonyl N-heterocyclic carbene (NHC) complex [(IPr)2Co2(CO)6] (IPr = 1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidene) as catalyst. This cobalt catalyst effects both alkyl- aryl-substituted variety good functional group compatibility, furnishing high yields α/β Mechanistic study revealed stoichiometric PhC≡CH HSiEt3 can furnish dinuclear alkyne mononuclear silyl complexes [(IPr)(CO)2Co(μ–η2:η2-HCCPh)Co(CO)3], [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)2(IPr)], [(IPr)Co(CO)3(SiEt3)], respectively. Both bridging react yield α-triethylsilyl styrene effect catalytic reaction. However, mono(NHC) [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)3] exhibits higher activity over di(NHC)-dicobalt complexes. The [(IPr)Co(CO)3(SiEt3)] ineffective catalyzing Deuterium labeling experiments PhC≡CD DSiEt3 indicates syn-addition nature absence deuterium scrambling products formed reaction mixture HSi(OEt)3 hints species less likely in-cycle species. These observations, addition evident nonsymmetric Co2C2-butterfly core structure [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)3], point out mono(IPr)-dicobalt genuine catalysts cobalt-catalyzed α selectivity system originates joint play coordinate Co(μ-η2:η2-HCCR′)Co mode steric demanding IPr ligand.

Language: Английский

Citations

64
Phenanthroline-imine ligands for iron-catalyzed alkene hydrosilylation DOI Creative Commons
Wei Sun, Mingpeng Li,

Lu-Jie Li

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(9), P. 2721 - 2728

Published: Jan. 1, 2022

Iron-catalyzed organic reactions have been attracting increasing research interest but still serious limitations on activity, selectivity, functional group tolerance, and stability relative to those of precious metal catalysts. Progress in this area will require two key developments: new ligands that can impart reactivity iron catalysts elucidation the mechanisms catalysis. Herein, we report development novel 2-imino-9-aryl-1,10-phenanthrolinyl complexes catalyze both

Language: Английский

Citations

52
Recent Advances in the Functionalization of Terminal and Internal Alkynes DOI

Arti Ramani,

Bhargav Desai,

Monak Patel

et al.

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(5)

Published: March 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Language: Английский

Citations

43
Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization DOI Open Access
Li Li, Wei‐Sheng Huang, Zheng Xu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1654 - 1687

Published: May 4, 2023

Language: Английский

Citations

37
NiII-Catalyzed Enantioselective Anti-Markovnikov Hydrophosphination of Unactivated Alkynes DOI

Wei-Han Wang,

Yue Wu,

Peng-Jia Qi

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6994 - 7001

Published: May 9, 2023

A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio- enantioselectivity easily derivatized to structurally diverse chiral compounds. Mechanistic studies on both Ni0-catalyzed Markovnikov addition NiII-catalyzed have been carried out combining experimental computational methods. In the Ni0 system, an allyl nickel complex as catalyst resting state whose structure unambiguously determined single-crystal XRD analysis. sequential hydrometallation, ligand exchange, reductive elimination mechanism elucidated corroboratively DFT calculations. cationic secondary serves active catalyst. migratory insertion protonation sequence operative accomplish hydrophosphination.

Language: Английский

Citations

26