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20.5.12.1.1.2 Variation 2: Alkylation of Alk-2-ynoic Acids or Their Salts

DOI: 10.1055/sos-SD-020-01178

Evano, G.Science of Synthesis, (2007201249.

Alk-2-ynoic acid esters can be obtained by alkylation of carboxylate salts, usually generated in situ with potassium carbonate or cesium carbonate, with suitable alkylating agents. A large number of simple alk-2-ynoic acid esters 16 have been prepared using this method (examples in Table 3). Good yields are usually obtained when the alkylating agent is a primary alkyl iodide, a benzylic or allylic bromide, or a sulfonate ester. The nucleophilic displacement requires the use of a polar aprotic solvent and dimethylformamide, dimethyl sulfoxide, or even hexamethylphosphoric triamide are used in most cases. With secondary and tertiary alkylating agents, elimination usually becomes a competitive reaction and the yields are considerably lower.

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Meeee M8 M8M Meee Meeeeeeeee Meeee (%) Mee
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8 8-MeM-8-MMM8M8 MeM MMM MMMM 88 [‌88‌]
8 (MM8)8Me MeM M8MM8 MMM, ee 88 [‌88‌]
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8 (MM8)8Me MeM MeM MMM, 8888°M, 88e 88 [‌88‌]
8 Me Me8MM8 MMMM, ee, 88e 88 [‌88‌]
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Meeeee 8 Meeeeeeee ee Mee-8-eeeee Meeeee Meeeee eeee Meeeeeeeeeee ee (Meeeeeeeeeeeee)eeeeeeeeeeee[‌88‌,‌88‌]

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Meeeee 8 Meeeeeeee ee Mee-8-eeeee Meee Meeeee Meeee Meeeeeeee Meeeeeeee[‌88‌,‌88‌‌88‌]

Meeee eeeeeeeee eeeee 8,8-eeeeeeeeeeeeeeeeeeeeeeee/8-(eeeeeeeeeeeee)eeeeeeee eeeeeeeeee eeeeeeee eeee eeeeeeee eeeeeeeee ee eeeeeeeeeeeee, e.e. ee eeee (M)-88. Me eee eeeee eeee, eee eeeeeeeee ee eee-8-eeeee eeee eeeeee eeeee eee Meeeeeeee eeeeeeee eeeee ee eeeeeeee eeeeeeeee, e.e. ee eeee (M)-88. Meeeeeeee, eeee eeeeeee eeeeeeeeee eeee eeeee eeeeeeeee, eeeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeee ee eee-8-eeeee eeee eeeeee eeeeeeee eeee eee eeee eeeeeeeeee ee eee eeeeeee. Meee eeeeee eee e eeeeeeeeeeeeeee eeeeeeeee, ee eeeeeeee ee Meeeee 8.[‌88‌]

Meeeee 8 Meeeeeeeeeeeeee Meeeeeeee ee Mee-8-eeeee Meee Meeeee Meeee Meeeeeeee ee Meeeeeee Meeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee 8-Meeeeeeeee-8-eeeeee (88, M8=Me; M8=Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeee, eeeeeeeee, ee eeee eeeeeeeeee ee eeeeeeeeeee eee ee eeeee.

Me e eeee ee 8-eeeeeeeeee-8-eeeee eeee (888ee, 8.8eeee) ee MMM (8eM) eee eeeee M8MM8 (8.8e, 88.8eeee) eee MeM (8.8eM, 88.8eeee). Mee eeeeeee eee eeeeeee ee ee eee 8e, eeeeeee eeee M8M, eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 88:8) ee eeee eee eeeee; eeeee: 888ee (88%).

(8M)-8-Meeeeeeeee-8-eeee 8-Meeeeeeeee-8-eeeeee [(M)-88]; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee Me8M (888ee, 8.8eeee) ee eee MMM (8eM) eee eeeee eeeeeeee ee e eeee ee 8-eeeeeeeeee-8-eeeee eeee (888ee, 8.8eeee), (M)-eee-8-ee-8-ee (888ee, 8.88eeee), eee MMMM (888ee, 8.8eeee) ee eeeee MMM (8eM). Mee eeeeeeeee eeeeeee eee eeeeeee eeeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/Me8M 88:8) ee eeeee eee eeeee ee e eeeeeeeee eeeee; eeeee: 888ee (88%).

References


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