Gram-Scale Robust Synthesis of 1-Chloro-2,3-dimethyl-4-phenylnaphthalene: A Promising Scaffold with Three Contiguous Reaction Positions

Kento Moriguchi; Taro Kono; Shinzo Seko; Yoo Tanabe

doi:10.1055/s-0040-1706471

Synthesis, Table of Contents

Synthesis 2020; 52(24): 3811-3817
DOI: 10.1055/s-0040-1706471

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Gram-Scale Robust Synthesis of 1-Chloro-2,3-dimethyl-4-phenylnaphthalene: A Promising Scaffold with Three Contiguous Reaction Positions

Kento Moriguchi

,

Taro Kono

,

Shinzo Seko

,

Yoo Tanabe∗

Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, Japan Email: tanabe@kwansei.ac.jp

› Author Affiliations

Abstract

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Abstract

A three-step reaction sequence for the gram-scale synthesis of 1-chloro-2,3-dimethyl-4-phenylnaphthalene was developed. (i) Stereoselective dichlorocarbene addition to methyl angelate afforded methyl (1S*,3S*)-2,2-dichloro-1,3-dimethylcyclopropane-1-carboxylate (78% yield, >98% purity, distillation). (ii) Addition reaction of two molar amounts of PhLi afforded (1S*,3S*)-2,2-dichloro-1,3-dimethylcyclopropyldiphenylmethanol (81% yield, >98% purity, recrystallization). (iii) Key SnCl₄-mediated benzannulation produced the desired product (83% yield, >98% purity, recrystallization) with three contiguous reaction sites. Five derivatization examples including benzylic reactions and cross-couplings at the pendant Cl-position are demonstrated. Some relevant distinctive benzannulations are also discussed.

Key words

gem-dichrolocyclopropane - benzannulation - naphthalene - gram-scale - benzylic - cross-coupling partners

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References

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