Open AccessOxa- and Azabenzonorbornadienes as Electrophilic Partners under Photoredox/Nickel Dual Catalysis
Author(s) -
Youran Luo,
Álvaro GutiérrezBonet,
Jennifer K. Matsui,
Madeline Rotella,
Ryan Dykstra,
Osvaldo Gutiérrez,
Gary A. Molander
Publication year - 2019
Publication title -
acs catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 4.898
H-Index - 198
ISSN - 2155-5435
DOI - 10.1021/acscatal.9b02458
Subject(s) - regioselectivity , chemistry , reductive elimination , electrophile , nucleophile , catalysis , alkyl , oxidative addition , photoredox catalysis , combinatorial chemistry , alcohol , oxidative coupling of methane , migratory insertion , organic chemistry , photocatalysis
Herein, the introduction of oxa- and azabenzonorbornadienes into photoredox/nickel dual catalysis in a regioselective and diastereoselective transformation is disclosed. The inherent advantages of this dual catalytic system allow the use of alkyl motifs forming exclusively cis -1,2-dihydro-1-naphthyl alcohol backbones using readily accessible 4-alkyl-1,4-dihydropyridines (DHPs). Whereas previous studies have emphasized the use of nucleophilic organometallic coupling partners, this protocol grants access to a rather unexplored core featuring alkyl residues, while avoiding the use of highly reactive organometallic species (i.e., M = Al, Mg, Li, Zn, Zr). DFT calculations support a oxidative addition/reductive elimination mechanism, followed by a Curtin-Hammett scenario that controls the regioselectivity of the process, unlike previously reported transformations that proceed via a carbometalation/ β -oxygen elimination mechanism.