Metal Carbene-Directed Intramolecular Vinylogous Reactions of Vinyldiazoacetates

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-10-25 DOI:10.1021/acscatal.4c05839

Marlyn S. Rada, Dmitry M. Bystrov, Diana Navarrete Carriola, Daniel Wherritt, Michael P. Doyle

引用次数: 0

Abstract

Intramolecular addition reactions of electrophilic metallovinylcarbenes with nucleophiles that do not have access to the carbene center undergo addition to the vinylogous position, forming products that rely on subsequent transformations of vinylmetal intermediates. Catalytic addition to a carbon-carbon double bond elicits the formation of an intermediate carbocation whose proton loss causes protodemetalation of the vinylmetal intermediate. Addition to the azido group results in the formation of aliphatic 1,2,3-triazines by [3 + 3]-cycloaddition. Catalytic intramolecular reactions with a carbamate nucleophile yield a carbonyl ylide whose loss of isobutylene produces oximidovinyl-oxazolidinone esters with high enantioselectivity. Comparisons are made between rhodium, copper, gold, and silver catalysts

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金属碳引导的乙烯基二氮乙酸酯分子内乙烯基反应

亲电金属乙烯基萘与无法进入碳烯中心的亲核物发生分子内加成反应时，会在乙烯基位置发生加成反应，形成依赖乙烯基金属中间体后续转化的产物。碳碳双键的催化加成反应会形成一个中间碳位体，其质子损失会导致乙烯基金属中间体的原脱醛作用。叠氮基团的加成导致通过 [3 + 3] 环加成反应生成脂肪族 1,2,3 三嗪。与氨基甲酸酯亲核剂的分子内催化反应产生了羰基醯胺，失去异丁烯的羰基醯胺会产生具有高对映体选择性的草酰亚胺基噁唑烷酮酯。铑、铜、金和银催化剂之间的比较

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.