872415-75-3Relevant articles and documents
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.
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.