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32.5.3.2.2.3.1 Additions of Alcohols to Alkynes under Basic Conditions

DOI: 10.1055/sos-SD-132-00059

Bartels, F.; Zimmer, R.; Christmann, M.Science of Synthesis Knowledge Updates, (20173243.

In the last decades, vinyl ethers have become increasingly important substrates in organic reactions such as cycloadditions,[‌57‌] Claisen rearrangements,[‌58‌] cyclopropanations,[‌59‌] and hydroformylation reactions.[‌60‌] Therefore, it is not surprising that several methods have been developed for their synthesis. Besides classical processes such as Reppe’s high-pressure vinylation, vinylation using expensive palladium catalysts, or transetherifications catalyzed by toxic mercury salts, an effective yet simple method has been developed applying superbasic conditions (alkali metal hydroxide in polar aprotic solvent). As shown in Scheme 17, alcohols 47 bearing either a pyrrole, tetrahydro-1H-indole, or hexahydrocyclohepta[b]pyrrole moiety react smoothly under an acetylene atmosphere and in presence of sodium hydroxide in dimethyl sulfoxide at 100 °C.[‌31‌] The desired vinyl ethers 48 are obtained in good to excellent yields.

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M M Me M 88 [‌88‌]
M Me Me M 88 [‌88‌]
M Me Me M 88 [‌88‌]
M (MM8)8 M 88 [‌88‌]
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M MM(Me)(MM8)8 M 88 [‌88‌]
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M8 M8 M8 Meee Meeeeeeeee Meeee (%) Mee
MM8Me MM=MM8 M MMMMM (88 eee%) MM8Me8, ee, 8.8 e 88 [‌88‌]
MM8Me (M)-MM=MMMe M MMMMM (88 eee%) MM8Me8, ee, 8.8 e 88 [‌88‌]
MM8Me (M)-MM=MMMe M MMMMM (88 eee%) MM8Me8, ee, 8.8 e 88 [‌88‌]
MM8Me (M,M)-MM=MMMM=MMMe M MMMMM (88 eee%) MM8Me8, ee, 8.8 e 8 [‌88‌]
MM8Me Me MM=MM8 MMMMM (88 eee%) MMM, ee, 8 e 88 [‌88‌]
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MM8Me M≡MM (MM8)8Me Me8M (88 eee%) MM8Me8, 8 °M, 88 eee eeeeee [‌88‌]
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M8 Meeee (%) Mee
M 88 [‌88‌]
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8-[8-(Meeeeeee)eeeee]-8M-eeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

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