25570-02-9Relevant articles and documents
Discovery and mechanistic investigation of Pt-catalyzed oxidative homocoupling of benzene with PhI(OAc)2
Abu-Omar, Mahdi M.,Nabavizadeh, S. Masoud,Niroomand Hosseini, Fatemeh,Park, Chan,Wu, Guang
supporting information, p. 2477 - 2486 (2020/03/05)
We present a Pt-catalyzed direct coupling of benzene to biphenyl. This catalytic reaction employs a cyclometalated platinum(ii) complex [PtMe(bhq)(SMe2)] (bhq = benzo[h]quinolate) with PhI(OAc)2 as an oxidant and does not require an acid, a co-catalyst or a solvent. The reaction kinetics and characterization of potential catalytic species are reported. The reaction is first-order in Pt and second-order in benzene, which implicates the second C-H activation step as rate-determining. A Pt(ii)/Pt(iv) catalytic cycle is suggested. The reaction commences by oxidation of the Pt(ii) complex to give the platinum(iv) species [Pt(bhq)(SMe2)(OAc)2](OAc) followed by C-H activation of benzene to afford the intermediate [PtPh(bhq)(SMe2)(OAc)](OAc) concurrently with the release of HOAc. A second benzene molecule reacts similarly to give the diphenyl intermediate [PtPh2(bhq)(SMe2)](OAc). C-C bond forming reductive elimination ensues to regenerate Pt(ii) and complete the catalytic cycle. The proposed mechanism has been examined by DFT computations, which provide support to experimental findings.
Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
supporting information, p. 6225 - 6229 (2013/07/05)
Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright
Base-catalyzed dehydrogenative Si-o coupling of dihydrosilanes: Silylene protection of diols
Grajewska, Agnieszka,Oestreich, Martin
supporting information; experimental part, p. 2482 - 2484 (2010/11/18)
The direct dehydrogenative coupling of 1,3- and 1,4-diols and dihydrosilanes is efficiently catalyzed by CsO(10 mol%), cleanly affording six- and seven-membered 1,3-dioxo-2-silacycles with dihydrogen as the sole by-product. Conversely, 1,2-diols do not yield the expected 1,3-dioxo-2- silacyclopentanes, essentially forming cyclic disiloxanes instead. Aside from the synthetic convenience, the procedure itself is also useful for straight-forward diol derivatization prior to GLC analysis. Georg Thieme Verlag Stuttgart · New York.