title: Transposed Paternò-Büchi Reaction.
abstract: A complementary strategy of utilizing ππ* excited state of alkene instead of nπ* excited state of the carbonyl chromophore in a "transposed Paternò-Büchi" reaction is evaluated with atropisomeric enamides as the model system. Based on photophysical investigations, the nature of excited states and the reactive pathway was deciphered leading to atropselective reaction. This new concept of switching of excited-state configuration should pave the way to control the stereochemical course of photoreaction due to the orbital approaches required for photochemical reactivity.
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58108, United States.
authors.forename: Elango
authors.identifier: 0000-0002-7995-6894
authors.initials: E
authors.lastname: Kumarasamy
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58108, United States.
authors.forename: Ramya
authors.initials: R
authors.lastname: Raghunathan
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58108, United States.
authors.forename: Sunil Kumar
authors.initials: SK
authors.lastname: Kandappa
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai, 400076. India.
authors.forename: A
authors.initials: A
authors.lastname: Sreenithya
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027, United States.
authors.forename: Steffen
authors.initials: S
authors.lastname: Jockusch
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai, 400076. India.
authors.forename: Raghavan B
authors.identifier: 0000-0002-6484-2878
authors.initials: RB
authors.lastname: Sunoj
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58108, United States.
authors.forename: J
authors.identifier: 0000-0002-0446-6903
authors.initials: J
authors.lastname: Sivaguru