35448-14-7Relevant articles and documents
Metal-, Photocatalyst-, and Light-Free Minisci C-H Alkylation of N-Heteroarenes with Oxalates
Dong, Jianyang,Wang, Zhen,Wang, Xiaochen,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
, p. 7532 - 7540 (2019/06/14)
Herein, we report a mild protocol for metal-, photocatalyst-, and light-free Minisci C-H alkylation reactions of N-heteroarenes with alkyl oxalates derived from primary, secondary, and tertiary alcohols. The protocol uses environmentally benign persulfate
Alcohols as Latent Coupling Fragments for Metallaphotoredox Catalysis: Sp3-sp2 Cross-Coupling of Oxalates with Aryl Halides
Zhang, Xiaheng,MacMillan, David W.C.
supporting information, p. 13862 - 13865 (2016/11/06)
Alkyl oxalates, prepared from their corresponding alcohols, are engaged for the first time as carbon radical fragments in metallaphotoredox catalysis. In this report, we demonstrate that alcohols, native organic functional groups, can be readily activated with simple oxalyl chloride to become radical precursors in a net redox-neutral Csp3-Csp2 cross-coupling with a broad range of aryl halides. This alcohol-activation coupling is successfully applied to the functionalization of a naturally occurring steroid and the expedient synthesis of a medicinally relevant drug lead.
Catalytic phosphorus(V)-mediated nucleophilic substitution reactions: Development of a catalytic appel reaction
Denton, Ross M.,An, Jie,Adeniran, Beatrice,Blake, Alexander J.,Lewis, William,Poulton, Andrew M.
, p. 6749 - 6767 (2011/10/02)
Catalytic phosphorus(V)-mediated chlorination and bromination reactions of alcohols have been developed. The new reactions constitute a catalytic version of the classical Appel halogenation reaction. In these new reactions oxalyl chloride is used as a consumable stoichiometric reagent to generate the halophosphonium salts responsible for halogenation from catalytic phosphine oxides. Thus, phosphine oxides have been transformed from stoichiometric waste products into catalysts and a new concept for catalytic phosphorus-based activation and nucleophilic substitution of alcohols has been validated. The present study has focused on a full exploration of the scope and limitations of phosphine oxide catalyzed chlorination reactions as well as the development of the analogous bromination reactions. Further mechanistic studies, including density functional theory calculations on proposed intermediates of the catalytic cycle, are consistent with a catalytic cycle involving halo- and alkoxyphosphonium salts as intermediates.
