872415-75-3Relevant academic research and scientific papers
Base-Promoted C-O Bond Cleavage of Primary Alcohols by Iridium(III) Porphyrin Chloride
Bian, Yongjun,Qu, Xingyu,Chan, Kin Shing
supporting information, p. 1376 - 1383 (2020/04/20)
Various Ir(por)-benzyls and Ir(por)-alkyls (por = porphyrinato dianion ligand) were successfully synthesized with benzyl and 1° alkyl alcohols by C-O bond cleavage with Ir(ttp)(CO)Cl (ttp = 5,10,15,20-tetraphenylporphyrinato dianion) in alkaline media. The alkylation products were afforded in up to 92% yields. Mechanistic investigations suggest that both the Ir(ttp)- anion and Ir(ttp)H are key intermediates via a hydrogen-borrowing pathway.
Alkyl Carbon-Oxygen Bond Cleavage of Aryl Alkyl Ethers by Iridium-Porphyrin and Rhodium-Porphyrin Complexes in Alkaline Media
Chen, Chen,Chan, Kin Shing
, p. 3456 - 3464 (2017/10/03)
Alkyl C-O bond cleavage in aryl alkyl ethers was achieved with Rh(ttp)Cl (1a; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) together with competitive alkyl C-H bond activation in alkaline media. In contrast, selective alkyl C-O bond cleavage occurred with the iridium-porphyrin Ir(ttp)(CO)Cl (1b)/KOH. Mechanistic investigations indicate the coexistence of MI(ttp)- and M2II(ttp)2 (M = Rh, Ir) under basic conditions. With a weaker Rh(ttp)-Rh(ttp) bond, RhII(ttp)· metalloradical exists in an appreciable amount to cleave the alkyl C-H bond, competing with the alkyl C-O bond cleavage via RhI(ttp)-. In contrast, the more nucleophilic IrI(ttp)- cleaves the alkyl C-O bond exclusively.
User-friendly aerobic reductive alkylation of iridium(III) porphyrin chloride with potassium hydroxide: Scope and mechanism
Zuo, Huiping,Liu, Zhipeng,Yang, Wu,Zhou, Zhikuan,Chan, Kin Shing
supporting information, p. 20618 - 20625 (2015/12/04)
Alkylation of iridium 5,10,15,20-tetrakistolylporphyrinato carbonyl chloride, Ir(ttp)Cl(CO) (1), with 1°, 2° alkyl halides was achieved to give (ttp)Ir-alkyls in good yields under air and water compatible conditions by utilizing KOH as the cheap reducing agent. The reaction rate followed the order: RCl N2 pathway by [IrI(ttp)]-. Ir(ttp)-adamantyl was obtained under N2 when 1-bromoadamantane was utilized, which could only undergo bromine atom transfer pathway. Mechanistic investigations reveal a substrate dependent pathway of SN2 or halogen atom transfer.
Base-promoted selective activation of benzylic carbon-hydrogen bonds of toluenes by iridium(III) porphyrin
Cheung, Chi Wai,Chan, Kin Shing
, p. 3043 - 3055 (2009/02/05)
K2CO3 and NaOPh promoted the rate of benzylic carbon-hydrogen bond activation (BnCHA) of toluenes with iridium(III) porphyrin carbonyl chloride (Ir(ttp)Cl(CO)) to give iridium porphyrin benzyls in high yields. Mechanistic studies sug
