title: Orbital Crossings Activated through Electron Injection: Opening Communication between Orthogonal Orbitals in Anionic C1-C5 Cyclizations of Enediynes.
abstract: Generally, the long-range electronic communication between spatially orthogonal orbitals is inefficient and limited to field and inductive effects. In this work, we provide experimental evidence that such communication can be achieved via intramolecular electron transfer between two degenerate and mutually orthogonal frontier molecular orbitals (MOs) at the transition state. Interaction between orthogonal orbitals is amplified when the energy gap between these orbitals approaches zero, or at an "orbital crossing". The crossing between two empty or two fully occupied MOs, which do not lead to stabilization, can be "activated" when one of the empty MOs is populated (i.e., electron injection) or one of the filled MOs is depopulated (i.e., hole injection). In reductive cycloaromatization reactions, such crossings define transition states with energies defined by both the in-plane and out-of-plane π-systems. Herein, we provide experimental evidence for the utility of this concept using orbital crossings in reductive C1-C5 cycloaromatization reactions of enediynes. Communication with remote substituents via orbital crossings greatly enhances regioselectivity of the ring closure step in comparison to the analogous radical cyclizations. We also present photophysical data pertaining to the efficiency of electron injection into the benzannelated enediynes.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Paul W
authors.initials: PW
authors.lastname: Peterson
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Nikolay
authors.initials: N
authors.lastname: Shevchenko
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Boris
authors.initials: B
authors.lastname: Breiner
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Mariappan
authors.initials: M
authors.lastname: Manoharan
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Forat
authors.initials: F
authors.lastname: Lufti
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Jess
authors.initials: J
authors.lastname: Delaune
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Margaret
authors.initials: M
authors.lastname: Kingsley
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Kirill
authors.initials: K
authors.lastname: Kovnir
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , 95 Chieftain Way, Tallahassee, Florida 32301, United States.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Alabugin