Boryl (Hetero)aryne Precursors as Versatile Arylation Reagents: Synthesis through C–H Activation and Orthogonal Reactivity
نویسندگان
چکیده
(Pinacolato)boryl ortho-silyl(hetero)aryl triflates are presented as a new class of building blocks for arylation. They demonstrate unique versatility by delivering boronate or (hetero)aryne reactivity chemoselectively in a broad range of transformations. This approach enables the unprecedented postfunctionalization of fluoride-activated (hetero)aryne precursors, for example, as substrates in transition-metal catalysis, and offers valuable new possibilities for aryl boronate postfunctionalization without the use of specialized protecting groups.
منابع مشابه
Synthetic and reaction chemistry of heteroatom stabilized boryl and cationic borylene complexes.
The synthesis, spectroscopic and structural characterization of the aryloxy and amino functionalized chloroboryl complexes (eta(5)-C(5)R(5))Fe(CO)(2)B(OMes)Cl (R = H, 2a ; R = Me, 3a) and (eta(5)-C(5)H(5))Fe(CO)(2)B(N(i)Pr(2))Cl (7a) are reported. Compound 2ais shown to be a versatile substrate for further boron-centred substitution chemistry leading to the asymmetric boryl complexes (eta(5)-C(...
متن کاملSelective S-arylation of 2-oxazolidinethiones and selective N-arylation of 2-benzoxazolinones/2-benzimidazolinones.
There exist three possible patterns for the reaction of cyclic 2-oxazolidinethione and 2-benzoxazolidinethione with arynes, namely (a) S-arylation, (b) N-arylation, and (c) aryne insertion into the thiocarbonyl group (C[double bond, length as m-dash]S). Our studies demonstrate that S-arylation wins out affording S-aryl dihydrooxazoles. In contrast, for related reactions of cyclic 2-benzoxazolin...
متن کاملPalladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes
Aryl-aryl bond formation constitutes one of the most important subjects in organic synthesis. The recent developments in direct arylation reactions forming aryl-aryl bond have emerged as very attractive alternatives to traditional cross-coupling reactions. Here, we describe a general palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to build a library of tetraphenylenes. Thi...
متن کاملStoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp2)-H arylation.
Based on the well-defined five-membered aryl gold(iii) complexes, [Au(tpy)X2] (3a and 3b) and [AuBr(Ph)(tpy)] (7), as well as the aryl gold(iii) complex [AuCl2(Ph)(tpy)] (8) (tpy = 2-(o-tolyl)pyridine) as reliable models, we present a detailed study of the mechanism for gold(iii)-catalyzed oxidative cross-coupling reactions between cycloaurable arenes and arylboronic acids. Here we report the d...
متن کاملGeneral Approach to the Synthesis of Prochiral Atropisomeric Biaryls
General approach to the synthesis of prochiral precursors of chiral atropisomeric biaryls based on several complementary methods has been developed. Biaryls were obtained in good to excellent yields depending on their structure and selected method of synthesis. Furthermore, we demonstrate a possibility of utilisation of the obtained compounds possessing 2 or 3 ortho substituents around the aryl...
متن کامل