Synthesis 2019; 51(07): 1561-1564
DOI: 10.1055/s-0037-1610356
psp
© Georg Thieme Verlag Stuttgart · New York

Practical Synthesis of Precursors of Cyclohexyne and 1,2-Cyclohexadiene

Ryo Nakura
,
Kazuki Inoue
,
Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe 657-8501, Japan   Email: [email protected]
,
Atsunori Mori
› Author Affiliations

This work was financially supported by JSPS KAKENHI Grant Numbers JP16K05774 in Scientific Research (C), JP16H01153 and JP18H04413 in the Middle Molecular Strategy, Creation of Innovation Centers for Advanced Interdisciplinary Research Areas (Innovative Bioproduction Kobe), Kawanishi Memorial ShinMaywa Education Foundation, and the Sasakawa Scientific Research Grant from The Japan Science Society.
Further Information

Publication History

Received: 16 October 2018

Accepted after revision: 14 November 2018

Publication Date:
11 January 2019 (online)


Abstract

This study investigated a practical method for regiocontrolled synthesis of precursors of strained cyclohexynes and 1,2-cyclohexadienes, which is a one-pot procedure consisting of a rearrangement of silyl enol ether and subsequent formation of the enol triflates. Triethylsilyl enol ether, derived from cyclohexanone, was treated with a combination of LDA and t-BuOK in n-hexane/THF to encourage the migration of the silyl group to generate an α-silyl enolate. Subsequently, the α-silyl enolate was reacted with Comins’ reagent to yield the corresponding enol triflate. Finally, the α-silylated trisubstituted lithium enolate for the synthesis of 1,2-cyclohexadiene precursor was isomerized in the presence of a stoichiometric amount of water for one hour at room temperature to exclusively provide tetrasubstituted lithium enolate for the synthesis of cyclohexyne precursor in one pot.

Supporting Information

 
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