title: A Simple and Versatile Amide Directing Group for C-H Functionalizations.
abstract: Achieving selective C-H activation at a single and strategic site in the presence of multiple C-H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, a directing group serves as a compass to guide the transition metal to C-H bonds by using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C-H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions: 1) Simplifying the directing group, 2) using common functional groups or protecting groups as directing groups, and 3) attaching the directing group to substrates via a transient covalent bond to render the directing group catalytic. This Review describes the rational development of an extremely simple and yet broadly applicable directing group for Pd(II) , Rh(III) , and Ru(II) catalysts, namely the N-methoxy amide (CONHOMe) moiety. Through collective efforts in the community, a wide range of C-H activation transformations using this type of simple directing group have been developed.
authors.affiliation: Department of Chemistry, The Scripps Research Institute (TSRI), 10550 N. Torrey Pines Road, La Jolla, CA, 92037, USA.
authors.forename: Ru-Yi
authors.initials: RY
authors.lastname: Zhu
authors.affiliation: Department of Chemistry, The Scripps Research Institute (TSRI), 10550 N. Torrey Pines Road, La Jolla, CA, 92037, USA.
authors.forename: Marcus E
authors.initials: ME
authors.lastname: Farmer
authors.affiliation: Department of Chemistry, The Scripps Research Institute (TSRI), 10550 N. Torrey Pines Road, La Jolla, CA, 92037, USA.
authors.forename: Yan-Qiao
authors.initials: YQ
authors.lastname: Chen
authors.affiliation: Department of Chemistry, The Scripps Research Institute (TSRI), 10550 N. Torrey Pines Road, La Jolla, CA, 92037, USA. yu200@scripps.edu.
authors.forename: Jin-Quan
authors.initials: JQ
authors.lastname: Yu
mesh_terms: D000577:Amides / Q000138:chemical synthesis / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D006838:Hydrocarbons / Q000138:chemical synthesis / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry
chemical_list: D000577:Amides; D006838:Hydrocarbons; D010165:Palladium; D002244:Carbon; D012428:Ruthenium; D006859:Hydrogen; D012238:Rhodium
keywords: C−H functionalization; directing groups; palladium; rhodium; ruthenium