Synthesis of [60]- and [70]Fullerene-Fused Tetrahydroquinoxaline Derivatives by Oxidative [4 + 2] Cycloaddition with Unusual Reactivity and Regioselectivity

Yue Sun; Cheng Qian; Thomas J Emge; Yanbang Li; William P Kopcha; Lu Wang; Jianyuan Zhang

doi:10.1021/acs.orglett.2c02494

Synthesis of [60]- and [70]Fullerene-Fused Tetrahydroquinoxaline Derivatives by Oxidative [4 + 2] Cycloaddition with Unusual Reactivity and Regioselectivity

Org Lett. 2022 Sep 9;24(35):6417-6422. doi: 10.1021/acs.orglett.2c02494. Epub 2022 Aug 29.

Authors

Yue Sun¹, Cheng Qian¹, Thomas J Emge¹, Yanbang Li¹, William P Kopcha¹, Lu Wang¹, Jianyuan Zhang¹

Affiliation

¹ Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 123 Bevier Rd, Piscataway, New Jersey 08854, United States.

PMID: 36036909
DOI: 10.1021/acs.orglett.2c02494

Abstract

The oxidative [4 + 2] reaction of o-phenylenediamine-derived disulfonamides with fullerene C₆₀ and C₇₀ is reported, in which electron-deficient reactants showed high reactivity. The reaction of C₇₀ exhibited unusual regioselectivity, yielding a [5,6]-adduct as the major product, which was characterized by ¹H, ¹³C NMR and single-crystal X-ray diffraction. DFT calculations revealed the reaction is an inverse-electron-demand Diels-Alder (IEDDA) reaction, and the [5,6]-adduct of C₇₀ is a kinetic product.