title: O-H hydrogen bonding promotes H-atom transfer from α C-H bonds for C-alkylation of alcohols.
abstract: The efficiency and selectivity of hydrogen atom transfer from organic molecules are often difficult to control in the presence of multiple potential hydrogen atom donors and acceptors. Here, we describe the mechanistic evaluation of a mode of catalytic activation that accomplishes the highly selective photoredox α-alkylation/lactonization of alcohols with methyl acrylate via a hydrogen atom transfer mechanism. Our studies indicate a particular role of tetra-n-butylammonium phosphate in enhancing the selectivity for α C-H bonds in alcohols in the presence of allylic, benzylic, α-C=O, and α-ether C-H bonds.
authors: Merck Center for Catalysis, Princeton University, Princeton, NJ 08544, USA.
authors: Jenna L
authors: JL
authors: Jeffrey
authors: Merck Center for Catalysis, Princeton University, Princeton, NJ 08544, USA.
authors: Jack A
authors: JA
authors: Terrett
authors: Merck Center for Catalysis, Princeton University, Princeton, NJ 08544, USA. dmacmill@princeton.edu.
authors: David W C
authors: DW
authors: MacMillan
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000478:Alkylation; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D010100:Oxygen / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D000644:Quaternary Ammonium Compounds; D002244:Carbon; D006859:Hydrogen; C009405:tetrabutylammonium; D010100:Oxygen