86769-71-3Relevant academic research and scientific papers
Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations
Hansen, Jorn,Li, Bo,Dikarev, Evgeny,Autschbach, Jochen,Davies, Huw M. L.
supporting information; experimental part, p. 6564 - 6571 (2010/03/03)
(Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O2CCF3)3(O2CCH3) was found to be approximately 1600 times less reactive than its homometallic analogue Rh2(O2CCF3)3(O 2CCH3) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.
Silver-catalyzed C-H insertion reactions with donor-acceptor diazoacetates
Lovely, Carl J.,Flores, Jaime A.,Meng, Xiaofeng,Dias, H. V. Rasika
experimental part, p. 129 - 132 (2009/05/30)
In this paper we describe the first examples of carbene transfer with donor-acceptor diazoacetates and the silver tris(pyrazolyl) borate complex {HB[3,5-(CF3)2Pz]3}Ag(THF). These reactions generally proceed in good yields
Highly selective metal catalysts for intermolecular carbenoid insertion into primary C-H bonds and enantioselective C-C bond formation
Thu, Hung-Yat,Tong, Glenna So-Ming,Huang, Jie-Sheng,Chan, Sharon Lai-Fung,Deng, Qing-Hai,Che, Chi-Ming
scheme or table, p. 9747 - 9751 (2009/05/30)
(Figure Presented) Primary C-H bond activation! A Rh complex of bis-pocket porphyrin I catalyzes carbenoid insertion into the C-H bonds of n-alkanes with a primary/secondary selectivity (per C-H bond) of up to 11.4:1 (see picture). Enantioselective secondary C-H bond functionalization catalyzed by a Rh complex of Halterman's chiral porphyrin features up to 93% ee. These reactions exhibit up to 6477 turnovers after the catalyst was recycled five times.
Enhancement of cyclopropanation chemistry in the silver-catalyzed reactions of aryldiazoacetates
Thompson, Janelle L.,Davies, Huw M. L.
, p. 6090 - 6091 (2008/02/07)
AgSbF6 is an effective catalyst for the reactions of donor/acceptor substituted carbenoids and shows a very different reactivity profile from the traditional rhodium-catalyzed reactions. Most notably, cyclopropanation of sterically hindered alk
The thionophosphate-thiolophosphate photoisomerization proceeds predominantly through a non-chain radical pathway. Synthetically viable benzylation of tetrahydrofuran, propan-2-ol and olefins
Yadav, Veejendra K.,Balamurugan, Rengarajan,Parvez, Masood,Yamdagni, Raghav
, p. 323 - 332 (2007/10/03)
The photoirradiation of thionophosphates, ROP(S)(OEt)2, derived from benzyl and vinylogously benzyl alcohols in CH3CN, with a Hanovia medium-pressure mercury lamp in a quartz vessel leads to the formation of the corresponding thiolophosphates, RSP(O)(OEt)2, through a non-chain radical pathway. This behavior of thionophosphates is unlike that of the related phosphates, which react through ionic dissociation-recombination processes. When the irradiation is conducted in solvents such as PriOH, THF and toluene, benzylation of these solvents takes place in synthetically respectable yields. Irradiation of thionophosphates in CH3CN leads to a convenient allylic benzylation of olefins.
Intermolecular cyclopropanation versus CH insertion in Rh(II)-catalyzed carbenoid reactions
Müller, Paul,Tohill, Sarah
, p. 1725 - 1731 (2007/10/03)
The product ratio of intermolecular insertion and cyclopropanation in transition metal-catalyzed diazo decompositions depends strongly upon the metal, its ligands and upon the substituents of the diazo compound. Ethyl diazoacetate (2a) reacts with cyclohexene (1) almost exclusively by cyclopropanation. However, diazomalonate (2d) and methyl 2-diazophenylacetate (2e) in the presence of Rh(II) catalysts exhibit a marked tendency towards allylic CH insertion. With 1,4-cyclohexadiene (6), methyl 2- diazophenylacetate (2e) in the presence of chiral Rh(II) catalysts affords the allylic insertion product 7 in almost quantitative yield and with up to 74% ee. (C) 2000 Elsevier Science Ltd.
O-SILYLATED ENOLATES IN ORGANIC SYNTHESIS: SULPHUR-MEDIATED ALKYLATION OF ESTERS WITH ALKENES.
Patel, Shailesh K.,Paterson, Ian
, p. 1315 - 1318 (2007/10/02)
O-Silylated ester enolates can be alkylated, under ZnBr2-catalysis, by the PhSCl-adducts of mono- and di-substituted alkenes to give γ-phenylthioesters, from which sulphur can be removed both reductively and oxidatively.This alkene carbosulphenylation rea
