☆ 4.7 Article

Nickel-Catalyzed Regioselective Cleavage of Csp2-S Bonds: Method for the Synthesis of Tri- and Tetrasubstituted Alkenes

JOURNAL OF ORGANIC CHEMISTRY (2016)

Journal

JOURNAL OF ORGANIC CHEMISTRY

Volume 81, Issue 8, Pages 3246-3255

Publisher

AMER CHEMICAL SOC

DOI: 10.1021/acs.joc.6b00203

Keywords

-

Categories

Chemistry, Organic

Funding

National Natural Science Foundation of China [21273068, 21373003, J1210040]
Fundamental Research Funds for the Central University, Hunan University

Ask authors/readers for more resources

Protocol

Community support

Reagent

Community support

Abstract

We describe here an efficient route for the synthesis of (Z)-vinylic sulfides 3 via the highly regio- and stereoselective coupling of (Z)-1,2-bis(aryl(alkyl)thio)alkenes and Grignard reagents over a Ni catalyst under mild conditions. (Z)-Vinylic sulfides 3 are important intermediates in the synthesis of tri- and tetrasubstituted alkenes that are important construction blocks for drugs and natural products. The directing organosulfur groups (SR) can be converted to diaryl(alkyl) disulfides (RSSR) using H2O2 as oxidant, hence avoiding the waste of sulfur resources. The protocol provides a general method that is highly regio- and stereoselective for the synthesis of a diversity of tri- and tetrasubstituted alkenes.

Authors

I am an author on this paper

Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.7

Not enough ratings

Secondary Ratings

Novelty

-

Significance

-

Scientific rigor

-

Rate this paper

Recommended

Article Chemistry, Organic

Photoredox-Catalyzed Dehydrogenative Csp3-Csp2 Cross-Coupling of Alkylarenes to Aldehydes in Flow

Oliver M. Griffiths, Henrique A. Esteves, Yiding Chen, Karin Sowa, Oliver S. May, Peter Morse, David C. Blakemore, Steven Ley

Summary: Executing photoredox reactions in flow can improve reaction concentration, reduce reaction time, achieve better yields, facilitate catalyst preparation, and expand substrate scope, demonstrating broad applicability.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Iron-Catalyzed Regioselective Alkenylboration of Olefins

Xiaolong Yu, Hongling Zheng, Haonan Zhao, Boon Chong Lee, Ming Joo Koh

Summary: A novel iron-catalyzed three-component synthesis method has been developed for the regioselective union of bis(pinacolato)diboron, an alkenyl halide, and an olefin to produce homoallylic boronates. The reaction can generate products with tertiary or quaternary carbon centers in up to 87% yield as single regioisomers with complete retention of the olefin stereochemistry. Selective formation of trisubstituted E-alkenylboronates from cyclopropylidene-containing substrates was also observed, revealing unique reaction attributes distinct from previously reported pathways.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Add to Collection

Article Multidisciplinary Sciences

Regioselective Ni-Catalyzed reductive alkylsilylation of acrylonitrile with unactivated alkyl bromides and chlorosilanes

Jinwei Sun, Yongze Zhou, Rui Gu, Xin Li, Ao Liu, Xuan Zhang

Summary: Here, the authors report a nickel-catalyzed method for the silylative alkylation of activated olefins using chlorosilanes and alkyl bromides. This approach enables the efficient synthesis of alkylsilanes with diverse structures and demonstrates good functional group tolerance. The method can also be applied for the functionalization of bioactive molecules.

NATURE COMMUNICATIONS (2022)

Add to Collection

Article Chemistry, Organic

Regioselective Disulfide-Catalyzed Photocatalytic Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes

Rodney A. Fernandes, Praveen Kumar, Amit Bhowmik, Dnyaneshwar A. Gorve

Summary: This research reveals a straightforward, effective, and environmentally friendly photocatalytic method for the regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes. The method features mild reaction conditions, ambient temperature, excellent regioselectivity, and compatibility with a wide range of functional groups.

ORGANIC LETTERS (2022)

Add to Collection

Article Chemistry, Organic

Stereoselective Palladium-Catalyzed C-F Bond Alkenylation of Tetrasubstituted gem-Difluoroalkenes via Mizoroki-Heck Reaction

Yanhui Wang, Gavin Chit Tsui

Summary: A highly diastereoselective Pd(0)-catalyzed Mizoroki-Heck reaction of gem-difluoroalkenes is reported. This reaction allows for cross-coupling of a C-F and C-H bond by reacting two different alkenes through a distinct pathway. Mono-fluorinated 1,3-diene products can be synthesized with control over each alkene's geometry and good functional group tolerance.

ORGANIC LETTERS (2023)

Add to Collection

Article Chemistry, Multidisciplinary

Regioselective and Enantioselective Copper-Catalyzed Hydroaminocarbonylation of Unactivated Alkenes and Alkynes

Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu

Summary: A novel method for constructing amide bonds through anti-Markovnikov hydroaminocarbonylation of unactivated alkenes has been developed. Copper catalysis, hydroxylamine electrophile reagents, and poly(methylhydrosiloxane) (PMHS) were used under mild conditions. The reaction showed a high degree of tolerance towards various functional groups and efficiently converted unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

Add to Collection

Article Chemistry, Multidisciplinary

Regioselective and Enantioselective Copper-Catalyzed Hydroaminocarbonylation of Unactivated Alkenes and Alkynes

Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu

Summary: This paper reports a general method for the anti-Markovnikov hydroaminocarbonylation of unactivated alkenes under mild conditions, using copper catalysis in combination with hydroxylamine electrophile reagents and poly(methylhydrosiloxane) (PMHS) as a cheap and environmentally friendly hydride source. The reaction tolerates a variety of functional groups and efficiently converts unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity (and high enantioselectivities/diastereoselectivities). Additionally, with minimal modification of the reaction conditions, alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation to alkyl amides.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

Add to Collection

Article Chemistry, Organic

Palladium(II)-Catalyzed Regioselective Hydrocarbofunctionalization of N-Alkenyl Amides: Synthesis of Tryptamine Derivatives

Nityananda Ballav, Suman Dana, Mahiuddin Baidya

Summary: The hydrocarbofunctionalization of allyl amines connected to the picolinamide directing group is developed under Pd(II) catalysis. The strategy is based on a nucleopalladation concept and can effectively produce indole derivatives. The synthetic utilities of this reaction, including the Pictet-Spengler cyclization and beta-carboline synthesis, were demonstrated. Mechanistic studies indicate that the reaction proceeds through an irreversible nucleopalladation pathway.

ORGANIC LETTERS (2022)

Add to Collection

Article Chemistry, Organic

Palladium(II)-Catalyzed Regioselective Hydrocarbofunctionalization of N-Alkenyl Amides: Synthesis of Tryptamine Derivatives

Nityananda Ballav, Suman Dana, Mahiuddin Baidya

Summary: This study introduces a Pd(II)-catalyzed hydrocarbofunctionalization method for allyl amines connected to the picolinamide directing group. The approach is based on the concept of nucleopalladation and a wide range of indoles effectively participate to produce valuable tryptamine derivatives with high yields. Synthetic utilities are showcased through substrate diversification bearing bioactive core, Pictet-Spengler cyclization, and beta-carboline synthesis. A mechanistic study suggests an irreversible nucleopalladation step, while protodepalladation follows a reversible pathway.

ORGANIC LETTERS (2022)

Add to Collection

Article Chemistry, Applied

Rh(III)-Catalyzed Csp2-Csp3 Bond Cleavage/Carbonylethylation of α-Indolyl Alcohols

Zhipeng Liu, Xinwei Hu, Can Yang, Haisheng Xie, Huanfeng Jiang, Wei Zeng

Summary: A new method was reported for the synthesis of 2-carbonylethylindole skeletons through Rh(III)-catalyzed Csp(2)-Csp(3) bond cleavage/carbonylethylation of alpha-indolyl alcohols with allylic alcohols. This transformation involved a cascade C-C bond cleavage/C-C bond formation, providing a novel approach for the construction of these complex skeletons.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Three-component regioselective carboamidation of 1,3-enynes via rhodium(iii)-catalyzed C-H activation

Lingheng Kong, Xi Han, Panjie Hu, Fen Wang, Xingwei Li

Summary: In this study, a rhodium-catalyzed regio- and stereoselective three-component carboamidation of 1,3-enynes was achieved using indoles and dioxazolones as functionalizing reagents. A wide range of multi-substituted skipped 1,4-dienes were synthesized in good yields and excellent stereoselectivity. The stereoselectivity is determined by the substrate, with bulky alkyne terminus favoring Z-selectivity and less hindered alkyne terminus predominantly giving the E-configured skipped diene.

CHEMICAL COMMUNICATIONS (2023)

Add to Collection

Article Chemistry, Organic

Copper-catalyzed regioselective 1,4-sulfonylcyanation of 1,3-enynes with sulfonyl chlorides and TMSCN

Yunhe Lv, Wanru Han, Weiya Pu, Jinhui Xie, Axue Wang, Mengyue Zhang, Jin Wang, Junrong Lai

Summary: A novel and practical copper-catalyzed reaction for 1,4-sulfonylcyanation of 1,3-enynes under mild conditions is described. The reaction provides efficient access to a variety of 5-sulfonylpenta-2,3-dienenitrile derivatives with excellent functional group tolerance and selectivity.

ORGANIC CHEMISTRY FRONTIERS (2022)

Add to Collection

Article Chemistry, Organic

TBAI-Catalyzed Regioselective Hydroxyperoxidation of 1-Aryl/Alkyl-1,3-dienes

Atul Kumar, Gulenur N. Khatun, Rodney A. Fernandes

Summary: An efficient, mild, and economical approach for the regioselective synthesis of 4-aryl/alkyl-1-peroxy-but-3-en-2-ols from 1-substituted-1,3-butadienes using hydroperoxides and catalyzed by TBAI has been achieved. This method is simple to operate, does not require dry conditions, and has excellent tolerance to a wide range of substrates, resulting in good yields of corresponding hydroxyperoxidates. Thus, an outstanding regioselective orthogonal dioxygenation in a diene system has been accomplished.

ORGANIC LETTERS (2023)

Add to Collection

Article Chemistry, Organic

Nickel-Catalyzed Regioselective Hydroamination of Ynamides with Secondary Amines

Xiao-Di Nie, Xiao-Li Han, Jian-Ting Sun, Chang-Mei Si, Bang-Guo Wei, Guo-Qiang Lin

Summary: This study introduces a novel method for the Ni(OTf)(2)-catalyzed hydroamination of ynamides with secondary amines, demonstrating high yields and excellent regioselectivity. The protocol shows good functional group tolerance for ynamides and a broad substrate scope of secondary aryl amines.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Nickel-Catalyzed Asymmetric Reductive Carbo-Carboxylation of Alkenes with CO2

Xiao-Wang Chen, Jun-Ping Yue, Kuai Wang, Yong-Yuan Gui, Ya-Nan Niu, Jie Liu, Chuan-Kun Ran, Wangqing Kong, Wen-Jun Zhou, Da-Gang Yu

Summary: The asymmetric reductive carbo-carboxylation of alkenes via nickel catalysis provides an efficient method for the synthesis of carboxylic acids with mild reaction conditions, wide substrate scope, and good selectivity. This approach opens up a new avenue for the total synthesis of chiral natural products using CO2.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Add to Collection

No Data Available

No Data Available

© Peeref 2019-2024. All rights reserved.