Latent Nucleophilic Carbenes DOI
A. P. MARCHENKO, Georgyi Koidan,

Anastasiya Hurieva

и другие.

The Journal of Organic Chemistry, Год журнала: 2021, Номер 87(1), С. 373 - 385

Опубликована: Дек. 13, 2021

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, trifluoromethane proceeded via insertion sp, sp2, sp3 CH bonds. carbene also reacted functional groups, such CHO, COR, CN at double or triple bonds, displaying high mobility of trimethylsilyl group. obtained silylformamidine be considered latent It prepared bulk quantities, stored, used when need arises. Calculation results predict similar behavior some other silylated related compounds.

Язык: Английский

Versatile Synthesis of α‐Oxygen Organoboron Compounds via Photo‐Induced Siloxycarbene DOI
Xiongxiong Lu,

Qingbin Zhao,

Dehai Cao

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(22), С. 2712 - 2716

Опубликована: Июль 9, 2024

Comprehensive Summary A novel method for synthesizing α‐oxygen organoboron compounds has been developed through acylsilane‐based carbene insertion reactions into C—B bonds. As coupling partners, readily available (alkenyl, allyl, and allenyl B(pin)) were employed. Based on the substrates, pure bonds or followed by a siloxy group rearrangement process (from carbon to boron) would occur, delivering with great diversities. Control experiments demonstrated that electronic effect of substituents mainly controlled process. Besides, no matter which isomer substrate ( Z E ) was used, reaction β‐aryl‐substituted alkenyl B(pin) affords both isomers products E, separable column chromatography). Trapping indicated triplet energy transfer involved.

Язык: Английский

Процитировано

2

Benzocyclobutenone Synthesis Exploiting Acylsilanes as Photofunctional Directing Groups DOI Creative Commons
Rowan L. Pilkington,

Hannah J. Ross,

Liselle Atkin

и другие.

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The visible-light irradiation of acylsilane tethered vinyl ketones promotes an intramolecular Stetter-type reaction

Язык: Английский

Процитировано

2

Cobalt-catalysed acyl silane directed ortho C–H functionalisation of benzoyl silanes DOI
Liselle Atkin, Daniel L. Priebbenow

Chemical Communications, Год журнала: 2022, Номер 58(90), С. 12604 - 12607

Опубликована: Янв. 1, 2022

Acyl silanes can be engaged as weakly coordinating directing groups in cobalt catalysed C–H functionalisation reactions to prepare benzoyl that are highly amenable subsequent synthetic manipulations yet inaccessible via existing methods.

Язык: Английский

Процитировано

10

Acyl silane directed Cp*Rh(iii)-catalysed alkylation/annulation reactions DOI
Daniel L. Priebbenow, Carol Hua

Chemical Communications, Год журнала: 2021, Номер 57(64), С. 7938 - 7941

Опубликована: Янв. 1, 2021

Studies into the Cp*Rh(iii)-catalysed hydroarylation of alkenes with aryl acyl silanes led to discovery a new synthetic strategy access unique silicon derived indene frameworks.

Язык: Английский

Процитировано

11

Latent Nucleophilic Carbenes DOI
A. P. MARCHENKO, Georgyi Koidan,

Anastasiya Hurieva

и другие.

The Journal of Organic Chemistry, Год журнала: 2021, Номер 87(1), С. 373 - 385

Опубликована: Дек. 13, 2021

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, trifluoromethane proceeded via insertion sp, sp2, sp3 CH bonds. carbene also reacted functional groups, such CHO, COR, CN at double or triple bonds, displaying high mobility of trimethylsilyl group. obtained silylformamidine be considered latent It prepared bulk quantities, stored, used when need arises. Calculation results predict similar behavior some other silylated related compounds.

Язык: Английский

Процитировано

11