title: Organic chemistry. Practical olefin hydroamination with nitroarenes.
abstract: The synthesis and functionalization of amines are fundamentally important in a vast range of chemical contexts. We present an amine synthesis that repurposes two simple feedstock building blocks: olefins and nitro(hetero)arenes. Using readily available reactants in an operationally simple procedure, the protocol smoothly yields secondary amines in a formal olefin hydroamination. Because of the presumed radical nature of the process, hindered amines can easily be accessed in a highly chemoselective transformation. A screen of more than 100 substrate combinations showcases tolerance of numerous unprotected functional groups such as alcohols, amines, and even boronic acids. This process is orthogonal to other aryl amine syntheses, such as the Buchwald-Hartwig, Ullmann, and classical amine-carbonyl reductive aminations, as it tolerates aryl halides and carbonyl compounds.
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Jinghan
authors.initials: J
authors.lastname: Gui
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Chung-Mao
authors.initials: CM
authors.lastname: Pan
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Ying
authors.initials: Y
authors.lastname: Jin
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Tian
authors.initials: T
authors.lastname: Qin
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Julian C
authors.initials: JC
authors.lastname: Lo
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA.
authors.forename: Bryan J
authors.initials: BJ
authors.lastname: Lee
authors.affiliation: Discovery Chemistry, Bristol-Myers Squibb, Princeton, NJ 08543, USA.
authors.forename: Steven H
authors.initials: SH
authors.lastname: Spergel
authors.affiliation: Discovery Chemistry, Bristol-Myers Squibb, Princeton, NJ 08543, USA.
authors.forename: Michael E
authors.initials: ME
authors.lastname: Mertzman
authors.affiliation: Discovery Chemistry, Bristol-Myers Squibb, Princeton, NJ 08543, USA.
authors.forename: William J
authors.initials: WJ
authors.lastname: Pitts
authors.affiliation: Chemical Development, Bristol-Myers Squibb, New Brunswick, NJ 08903, USA.
authors.forename: Thomas E
authors.initials: TE
authors.lastname: La Cruz
authors.affiliation: Chemical Development, Bristol-Myers Squibb, New Brunswick, NJ 08903, USA.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Schmidt
authors.affiliation: Kemxtree LLC, 1370 Hamilton Street, Somerset, NJ 08873, USA.
authors.forename: Nitin
authors.initials: N
authors.lastname: Darvatkar
authors.affiliation: Kemxtree LLC, 1370 Hamilton Street, Somerset, NJ 08873, USA.
authors.forename: Swaminathan R
authors.initials: SR
authors.lastname: Natarajan
authors.affiliation: Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037, USA. pbaran@scripps.edu.
authors.forename: Phil S
authors.initials: PS
authors.lastname: Baran