Rh-catalyzed decarbonylation of conjugated ynones via carbon–alkyne bond activation: reaction scope and mechanistic exploration via DFT calculations
نویسندگان
چکیده
The University of Texas at Austin, Departm Beijing National Laboratory of Molecular Bioorganic Chemistry and Molecular Eng University, Beijing, 100871, China Key Laboratory of Pesticide & Chemical B Chemistry, Central China Normal Universit † Electronic supplementary informa 10.1039/c5sc00584a ‡ Current address: Pzer Inc., Eastern P States. § AD and REW contributed equally. Cite this: Chem. Sci., 2015, 6, 3201
منابع مشابه
Rh-catalyzed decarbonylation of conjugated ynones via carbon–alkyne bond activation: reaction scope and mechanistic exploration via DFT calculations† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc00584a
In this full article, detailed development of a catalytic decarbonylation of conjugated monoynones to synthesize disubstituted alkynes is described. The reaction scope and limitation has been thoroughly investigated, and a broad range of functional groups including heterocycles were compatible under the catalytic conditions. Mechanistic exploration via DFT calculations has also been executed. T...
متن کاملMechanistic study of the rhodium-catalyzed carboxylation of simple aromatic compounds with carbon dioxide.
A detailed mechanism of the Rh(i)-catalyzed carboxylation of simple aromatic compounds via C-H bond activation was investigated. Kinetic studies with model compounds of the postulated key intermediates revealed that 14-electron complexes, RhMe(dcype) and RhPh(dcype), participated in the C-H bond activation step and the carboxylation step, respectively. Interestingly, the undesired carboxylation...
متن کاملMechanistic insights into the selective cyclization of indolines with alkynes and alkenes to produce six- and seven-membered 1,7-fused indolines via Rh(iii) catalysis: a theoretical study.
The coupling reaction mechanisms of the Rh(iii)-catalyzed redox-neutral C7-selective aryl C-H functionalization of indolines with alkynes and alkenes have been theoretically investigated with the aid of the density functional theory (DFT) calculations. Our calculation results indicate that the active catalyst in this system is the cationic species [Cp*Rh(OAc)]+ (2cat) instead of the neutral spe...
متن کاملGold-Catalyzed 1,3-Transposition of Ynones
An efficient, regioselective gold-catalyzed 1,3-transposition reaction of ynones and diynones has been developed. It was found that stereoelectronic (interrupted conjugation) and electronic (extended conjugation) factors could efficiently govern the regioselectivity of this thermodynamically controlled transformation. The produced conjugated diynones were efficiently transformed into diverse al...
متن کاملMechanistic study of the rhodium-catalyzed carboxylation of simple aromatic compounds with carbon dioxide† †Electronic supplementary information (ESI) available: Experimental details and crystallographic data in cif format. CCDC 1017905. For ESI and crystallographic data in CIF or other electronic formats see DOI: 10.1039/c6sc03838g Click here for additional data file. Click here for additional data file.
A detailed mechanism of the Rh(I)-catalyzed carboxylation of simple aromatic compounds via C–H bond activation was investigated. Kinetic studies with model compounds of the postulated key intermediates revealed that 14-electron complexes, RhMe(dcype) and RhPh(dcype), participated in the C–H bond activation step and the carboxylation step, respectively. Interestingly, the undesired carboxylation...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
دوره شماره
صفحات -
تاریخ انتشار 2015