Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

Yoshiya Sekiguchi; Jia Hao Pang; Jia Sheng Ng; Jiahua Chen; Kohei Watanabe; Ryo Takita; Shunsuke Chiba

doi:10.1021/jacsau.2c00487

Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

JACS Au. 2022 Nov 30;2(12):2758-2764. doi: 10.1021/jacsau.2c00487. eCollection 2022 Dec 26.

Authors

Yoshiya Sekiguchi¹, Jia Hao Pang¹, Jia Sheng Ng¹, Jiahua Chen¹, Kohei Watanabe², Ryo Takita^{2

3}, Shunsuke Chiba¹

Affiliations

¹ School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore 637371, Singapore.
² Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
³ School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan.

Abstract

Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center.