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Synthesis 2018; 50(21): 4313-4324
DOI: 10.1055/s-0037-1609561
DOI: 10.1055/s-0037-1609561
paper
tert-Butoxide-Assisted Structural Transformation of 2-Aza-1,3,5-trienes: Fast Track to 5-Ethynyl-2-vinyl- and 2,5-Divinyl-1,3-thiazoles
Further Information
Publication History
Received: 21 May 2018
Accepted after revision: 18 June 2018
Publication Date:
22 August 2018 (online)
Abstract
Treatment of 2-aza-1,3,5-trienes, methyl N-[2-alkoxy-1-(prop-2-ynylsulfanyl)buta-1,3-dienyl]- and methyl N-[1-(allylsulfanyl)-2-alkoxybuta-1,3-dienyl]iminoformates, which are easily obtained from lithiated alkoxyallenes, methoxymethyl isothiocyanate, and propargyl or allyl bromide, with t-BuOK or t-BuONa in DMSO–THF results in the formation of 5-ethynyl-2-vinyl- and 2,5-divinyl-1,3-thiazoles. The reactions are realized under mild conditions at ca. –30 °C for 30 minutes. An unprecedented structural transformation of the (prop-2-ynylsulfanyl)- and (allylsulfanyl)-substituted 2-aza-1,3,5-trienes into 1,3-thiazoles presumably occurs via α-deprotonation of the substituent at the sulfur atom (on the SCH2 group) followed by intramolecular [1,5]-cyclization at the imine group and aromatization (with elimination of MeOH).
Key words
alkoxyallenes - methoxymethyl isothiocyanate - 2-aza-1,3,5-trienes - deprotonation - intramolecular cyclization - aromatization - 5-ethynyl-2-vinyl-1,3-thiazoles - 2,5-divinyl-1,3-thiazolesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1609561.
- Supporting Information
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