title: Diverse ortho-C(sp2)-H Functionalization of Benzaldehydes Using Transient Directing Groups.
abstract: Pd-catalyzed C-H functionalizations promoted by transient directing groups remain largely limited to C-H arylation only. Herein, we report a diverse set of ortho-C(sp2)-H functionalizations of benzaldehyde substrates using the transient directing group strategy. Without installing any auxiliary directing group, Pd(II)-catalyzed C-H arylation, chlorination, bromination, and Ir(III)-catalyzed amidation, could be achieved on benzaldehyde substrates. The transient directing groups formed in situ via imine linkage can override other coordinating functional groups capable of directing C-H activation or catalyst poisoning, significantly expanding the scope for metal-catalyzed C-H functionalization of benzaldehydes. The utility of this approach is demonstrated through multiple applications, including late-stage diversification of a drug analogue.
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Xi-Hai
authors.initials: XH
authors.lastname: Liu
authors.affiliation: Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Hojoon
authors.initials: H
authors.lastname: Park
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Jun-Hao
authors.initials: JH
authors.lastname: Hu
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Hu
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Qun-Liang
authors.initials: QL
authors.lastname: Zhang
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Bao-Long
authors.initials: BL
authors.lastname: Wang
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Bing
authors.initials: B
authors.lastname: Sun
authors.affiliation: Department of Discovery Chemistry, Bristol-Myers Squibb Research and Development , 5 Research Parkway, Wallingford, Connecticut 06492, United States.
authors.forename: Kap-Sun
authors.initials: KS
authors.lastname: Yeung
authors.affiliation: School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology , Wuhan 430070, People's Republic of China.
authors.forename: Fang-Lin
authors.initials: FL
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
authors.forename: Jin-Quan
authors.identifier: 0000-0003-3560-5774
authors.initials: JQ
authors.lastname: Yu