117947-77-0Relevant articles and documents
Development and Mechanistic Studies of Iron-Catalyzed Construction of Csp2-B Bonds via C-O Bond Activation
Geng, Shasha,Zhang, Juan,Chen, Shuo,Liu, Zhengli,Zeng, Xiaoqin,He, Yun,Feng, Zhang
supporting information, p. 5582 - 5588 (2020/07/08)
Herein we describe an iron-catalyzed borylation of alkenyl and aryl carbamates through the activation of a C-O bond. This protocol exhibits high efficiency, a broad substrate scope, and the late-stage borylation of biorelevant compounds, thus providing potential applications in medicinal chemistry. Moreover, this method enables orthogonal transformations of phenol derivatives and also offers good opportunities for the synthesis of multisubstituted arenes. Preliminary mechanistic studies suggest that a FeII/FeIII catalytic cycle via a radical pathway might be involved in the reaction.
Experimental and computational study of the 1,5-o → n carbamoyl snieckus-fries-type rearrangement
Feberero, Claudia,Lopez, Carlos Silva,Sanz, Roberto,Sedano, Carlos,Suarez-Pantiga, Samuel
, p. 12561 - 12578 (2020/11/09)
The reactions of o-lithiated O-aryl N,N-diethylcarbamates with different C-N multiple bond electrophiles have been thoroughly studied. A 1,5-O → N carbamoyl shift, a new variation of the anionic Fries-type rearrangement, takes place when nitriles, imines, or alkylcarbodiimides are employed. In these cases, the carbamoyl group plays a dual role as a directing group, building up a variety of functional groups through the 1,5-O → N carbamoyl migration. On the other hand, the use of iso(thio)cyanates and arylcarbodiimides led to non-rearranged o-functionalized Oarylcarbamates. This reactivity was further computationally explored, and the governing factor could be traced back to the relative basicity of the alternative products (migrated vs nonmigrated substrates). This exploration also provided interesting insights about the degree of complexation of the lithium cations onto these substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed.
A copper-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide using molecular oxygen as the oxidant
Xiong, Wenfang,Qi, Chaorong,Guo, Tianzuo,Zhang, Min,Chen, Kai,Jiang, Huanfeng
supporting information, p. 1642 - 1645 (2017/06/05)
A Cu-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide is described for the first time in this paper. The reaction tolerates a wide range of functional groups, providing a convenient protocol for the synthesis of various O-aryl carbamates. The successful development of the transformation was enabled by the use of BF3·OEt2 as the promoter and molecular oxygen as the oxidant. Mechanistic studies suggested that the CuII carbamato complex is involved in the catalytic transformation.
Lithiation of a silyl ether: Formation of an ortho-fries hydroxyketone
Lo, Hong-Jay,Lin, Chin-Yin,Tseng, Mei-Chun,Chein, Rong-Jie
supporting information, p. 9026 - 9029 (2014/09/17)
A hydroxy-directed alkylation of an N,N-diethylarylamide using CIPE-assisted α-silyl carbanions (CIPE=complex-induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus-Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3-kinase (PI3K) inhibitor LY294002, are reported.
Beyond directed ortho metalation: Ru-catalyzed CAr-O activation/cross-coupling reaction by amide chelation
Zhao, Yigang,Snieckus, Victor
supporting information, p. 11224 - 11227 (2014/09/29)
Disclosed is a new, catalytic, and general methodology for the chemical synthesis of biaryl, heterobiaryl, and polyaryl molecules by the cross-coupling of o-methoxybenzamides with aryl boroneopentylates. The reaction is based on the activation of the unreactive C-OMe bond by the proximate amide directing group using catalytic RuH2(CO)(PPh3)3 conditions. A one-step, base-free coupling process is thereby established that has the potential to supersede the useful two-step directed ortho metalation/cross- coupling reaction involving cryogenic temperature and strong base conditions. High regioselectivity, orthogonality with the Suzuki-Miyaura reaction, operational simplicity, minimum waste, and convenient scale-up make these reactions suitable for industrial applications.
