Synthesis of naphthalene derivatives via nitrogen-to-carbon transmutation of isoquinolines.

Abstract

Heteroarene skeletal editing is gaining popularity in synthetic chemistry. Transmuting single atoms generates molecules that have distinctly varied properties, thereby fostering potent molecular exchanges that can be extensively used to synthesize functional molecules. Herein, we present a convenient protocol for nitrogen-carbon single-atom transmutations in isoquinolines, which is inspired by the Wittig reaction and enables easy access to substituted naphthalene derivatives. The reaction uses an inexpensive and commercially available phosphonium ylide as the carbon source to furnish a wide range of substituted naphthalenes. The key to the success of this transformation is the formation of a triene intermediate through ring opening, which undergoes 6π-electrocyclization and elimination processes to afford the naphthalene product. Furthermore, this strategy enables the facile synthesis of ¹³C-labeled naphthalenes using ¹³CH₃PPh₃I as a commercial ¹³C source and facilitates modifying the directing group for C─H functionalization.