Nickel-catalyzed remote and proximal Wacker-type oxidation DOI Creative Commons
Binbin Liu, Penghui Hu, Fangning Xu

et al.

Communications Chemistry, Journal Year: 2019, Volume and Issue: 2(1)

Published: Jan. 4, 2019

Abstract Wacker oxidation chemistry is widely applied to of olefins carbonyls in the synthesis pharmaceuticals, natural products, and commodity chemicals. However, this efficient internal highly selective unbiased without reliance upon suitable coordinating groups have remained significant challenges. Here we report a nickel-catalyzed remote Wacker-type where reactions occur at less-reactive sp 3 C–H sites presence priori more reactive ones through chain-walking mechanism with excellent regio- chemo- selectivity. This transformation has attractive features including use ambient air as sole oxidant, naturally-abundant nickel catalyst, polymethylhydrosiloxane hydride source room temperature, allowing for effective challenging olefins. Notably, approach enables direct access broad array complex, medicinally relevant molecules from structurally complex substrates chemical feedstocks.

Language: Английский

Chain Walking as a Strategy for Iridium-Catalyzed Migratory Amidation of Alkenyl Alcohols to Access α-Amino Ketones DOI
Yeongyu Hwang,

Seung Beom Baek,

Dongwook Kim

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 4277 - 4285

Published: Feb. 24, 2022

Catalytic carbon–nitrogen bond formation in hydrocarbons is an appealing synthetic tool to access valuable nitrogen-containing compounds. Although a number of approaches have been developed construct bifunctional α-amino carbonyl scaffold this realm, installation amino functionality at the remote and unfunctionalized aliphatic sites remains underdeveloped. Here we present tandem iridium catalysis that enables redox-relay amidation alkenyl alcohols via chain walking metal-nitrenoid transfer, which eventually offers new route various ketones with excellent regioselectivity. The virtue transformation unrefined isomeric mixture can be utilized as readily available starting materials lead regioconvergent amidation. Mechanistic investigations revealed reaction proceeds process involving two key components intermolecular nitrenoid transfer assistance hydrogen bonding, thus representing competence Ir for olefin migratory C–N coupling high efficiency exquisite selectivity.

Language: Английский

Citations

32
Transition-metal-catalyzed decarbonylation of carboxylic acids to olefins: exploiting acyl C–O activation for the production of high value products DOI
Xu Zhang, Frank Jordan, Michal Szostak

et al.

Organic Chemistry Frontiers, Journal Year: 2018, Volume and Issue: 5(16), P. 2515 - 2521

Published: Jan. 1, 2018

In this article, we review the recent developments in transition-metal-catalyzed decarbonylation of carboxylic acids to produce olefins by formal acyl C–O activation mechanism and discuss future challenges field.

Language: Английский

Citations

53
Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes DOI
Dao-Yong Zhu, Zhiwei Jiao, Yonggui Robin

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(13), P. 5341 - 5345

Published: Jan. 22, 2020

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5-aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary secondary anilines, indoline, benzylamines suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack

Language: Английский

Citations

48
Metal‐Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium‐Catalyzed Hydrosilylation/Cyclization of 1,n‐Dienes by Chain Walking DOI
Takuya Kochi,

Kazuya Ichinose,

Masayuki Shigekane

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(16), P. 5261 - 5265

Published: Feb. 12, 2019

Abstract Sequential formation of distant bonds in organic molecules was achieved for the palladium‐catalyzed hydrosilylation/cyclization various 1, n ‐dienes by chain walking metal catalyst. The reaction applicable to ‐dienes, including a 1,13‐diene, form cyclopentane ring as well carbon–silicon bond at remote site. use “nondissociative” provides fascinating strategy synthesis functionalize parts molecules, particular order, within catalytic cycle effectively moving reactive center from position.

Language: Английский

Citations

46
Nickel-catalyzed remote and proximal Wacker-type oxidation DOI Creative Commons
Binbin Liu, Penghui Hu, Fangning Xu

et al.

Communications Chemistry, Journal Year: 2019, Volume and Issue: 2(1)

Published: Jan. 4, 2019

Abstract Wacker oxidation chemistry is widely applied to of olefins carbonyls in the synthesis pharmaceuticals, natural products, and commodity chemicals. However, this efficient internal highly selective unbiased without reliance upon suitable coordinating groups have remained significant challenges. Here we report a nickel-catalyzed remote Wacker-type where reactions occur at less-reactive sp 3 C–H sites presence priori more reactive ones through chain-walking mechanism with excellent regio- chemo- selectivity. This transformation has attractive features including use ambient air as sole oxidant, naturally-abundant nickel catalyst, polymethylhydrosiloxane hydride source room temperature, allowing for effective challenging olefins. Notably, approach enables direct access broad array complex, medicinally relevant molecules from structurally complex substrates chemical feedstocks.

Language: Английский

Citations

45