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24.2.17.1.1.36 Method 36: Synthesis from Alkyne- and Allene-Substituted Ortho Amides

DOI: 10.1055/sos-SD-024-00566

Kantlehner, W.Science of Synthesis, (200624623.

Alkyne-substituted ortho amides of a wide structural variety are easily accessible. It is very likely that in solution the compounds dissociate into dialkylamide ions and ambident amidinium ions. With this assumption, the reactions of the ortho amide derivatives with CH2-acidic compounds to give ketene N,N-acetals can be readily explained. The CH2-acidic compound is deprotonated by the dimethylamide ion, and the carbanion thus formed preferentially attacks at C3 of the amidinium ion, and by a proton shift ketene N,N-acetals result (Scheme 110).

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Meeeee 888 Meeeeeee ee ee Meeeee-Meeeeeeeeee Meeee Meeee eeee MM8-Meeeee Meeeeeeee eeee Meeeeeeeeee Meeeeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeeee, eeeeee M,M-eeeeeee 888 eee ee eeeeeeee eeee eee eeeeeeee ee eeeeeeee MM-eeeeee eeeeeeeee, eeee ee eeeeeee eeeeeeeeeeeeee ee eeeee 8-eeeeeeeeeeeeeee, eeee eeeee eeeee 888 (Meeeee 888).[‌888‌] Me ee eeeeeee eeee e eeeeeeeeeeeeeee eeeeee eeeee eeee eeeeeeeee ee eee eeeeeeeee eeeeeeeeee eeeeee M,M-eeeeee.

Meeeee 888 Meeeeeee ee ee Meeeee-Meeeeeeeeee Meeee Meeee eeee Meeeeeee MM8-Meeeee Meeeeeeee[‌888‌]

Meeeee M,M-eeeeeee eeeeeeee ee eeeeeeeeeeee ee eeeeeee (8-eeeeeeeee)eeeeeeeeeee eee eeeee eeeee eeeeeeeeeee ee eeeeeeeeee-8-eeeee eeee, eeeeee eeeeeeeee ee eeeeeeee, eee eeee eeeeeee ee eeeeeee, ee eeee eeeeee ee eeeee-8,8-eeeeeee eeee.[‌8‌] Meeee eeeeeee eeeeeeeeeeeeee eee eeee eeeee.[‌888‌]

Meee eeeeeeeee eeeeee eeeee eeeee ee eeeeeee eeee eeeeeeeeeeeeeeeeeeeee eeeeeeee 88, e eeeeeee ee eeeeee-eeeeeeeeeee eeeee eeeeee 888 eee 888 eeeeeee. Meee eeeeeeeeee eeeeeee eeeeeeeee eeeeeeee eeee MM8-eeeeee eeeeeeeee ee eeee eeeeee M,M-eeeeeee 888 (Meeeee 888).[‌888‌]

Meeeee 888 Meeeeeee ee Meeeee-Meeeeeeeeee Meeee Meeeee eeee MM8-Meeeee Meeeeeeee[‌888‌]

Meeeee M,M-eeeeeee eee ee eeeeeeee eeee eee eeeeeeee ee eeeeeee-eeeeeeeeeee eeeee eeeeee eee eeeeeeeeeeeee eeeeeeee ee eeeeeeee ee eee eeeee eeeee eeeeeeee.[‌8‌,‌888‌,‌888‌,‌888‌] Mee eeeeeee, eee eeeeeeee ee eeeee eeeee 888 eeee ee eeeeee ee eeeeee eeeeeeeee eeeeeeee eee eeeeee M,M-eeeeee 888 ee 88% eeeee (Meeeee 888).[‌888‌]

Meeeee 888 Mee Meeeeeee ee Meeeee-Meeeeeeeeee Meeee Meeeee[‌8‌,‌888‌,‌888‌,‌888‌]

Meeeeee-eeeeeeeeeee eeeee eeeeee 888 eeeee eeee eeeeeeeeeeeeeeeeeeee ee eeee eeeeee M,M-eeeeeee 888, eeee eeeeeeee eee ee eeeeeeeeeee eeeeeeeeeeee (Meeeee 888).[‌888‌]

Meeeee 888 Meeeeeee ee Meeee Meeeee eeee Meeeeeeeeeeeeeeeeeee[‌888‌]

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Meeeee 888 Meeeeeee ee Meeee Meeeee eeee Meeeeeeeeeee[‌888‌]

Mee eeeeeeee ee eeeee eeeee eeeeeeeeeee ee eeeeeeeee eeee [e.e., 888 (M8=M)] eeee 8,8-eeeeeeeeeeeeeeeeeeeee 888 eeeeeee eeeeee M,M-eeeeeee [e.e., 888 (M8=M)], ee eeeee ee Meeeee 888.[‌888‌] Meeeeeeeeee [e.e., 888 (M8=eeee)] eeee eeeeee, eeee 8,8-eeeeeeeeeeeeeeeeeeeee eeee eeeeee eeee eeeeeeeeee eeeeeeeeeee ee 8-eeeeeeee-8-eeeee eeee [e.e., 888 (M8=eeee)].[‌888‌]

Meeeee 888 Meeeeeee ee Meeee Meeeee eeee 8,8-Meeeeeeeeeeeeeeeeeeee[‌888‌]

Mee eeeeeeeeee eeeeeeeeee ee eeeeeeeeee-8-eeeee eeee (e.e., 888) eeeee eeee eeeeeeeee ee eeee M,M-eeeeeeeeeeeeeeeeeeeeee 888, eeeeeee eee eeeeeeeee eeeeeeee eeee M-eeeeeeeeeeeeeee eeeeeeee eee eeeeee M,M-eeeeee 888 (Meeeee 888).[‌888‌] Mee eeeeee M,M-eeeeee 888, eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeeeee eeee eeeee eeeee 888, eeeeeeeee eeeeeee eeeeeeee eeee eee eeeee eeeee 888 ee eeee eee eeeeeeee 888 eeeeeeeeee eee eeeeee M,M-eeeeee eeeeeeee.[‌888‌] Meeee eeeee 888 eeee eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeeee ee eeeeeeeeeeeeeee ee eeeeeee eee eeeeee M,M-eeeeeee 888.[‌888‌]

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Meeeee M,M-eeeeeee eee eeee ee eeeeeeee eeee eee eeeeeeee ee eeeeee-eeeeeeeeeee eeeee eeeeee eeee eeeeeeee ee eeeeeeeeee eeeee. Mee eeeeeee, eee eeeeeeeeeeee ee eeeee eeeee 888 eeeeeeee eee eeeeee M,M-eeeeee 888 ee 88% eeeee (Meeeee 888).[‌888‌] Meeeee M,M-eeeeeee 888 eee ee eeeeeeee ee eeee eeeeee ee eee eeeeeeee ee eeeee eeeee 888 eeee 8,8- ee 8,8-eeeee.[‌888‌] Mee eeeeeeeee eeeeeeee ee eeeee eeeee 888 eeee eeeeee eeee eeeeeee e eeeeeee ee eeeeee M,M-eeeeee 888 eee eeeeeeee eeeeeee 888 ee 88 eee 88% eeeee, eeeeeeeeeeee.[‌888‌]

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Mee eeeeeeee ee eeeeeee-eeeeeeeeeee eeeee eeeeee eeee eeeeeeee eee ee eeee ee eeeeeee 8,8-eeeeeee-8-eeeeeeeeee-8-eee-8-eeeeeee. Mee eeeeeee, eee eeeeeeee ee eeeee eeeee eeeeeeeeeee ee 8-eeeeeeee-8-eeeee eeeee (e.e., 888) eeee eeeeee-8,8-eeeeeee eeeeeeee eeeeee M,M-eeeeeee (e.e., 888), ee eeeee ee Meeeee 888.[‌888‌]

Meeeee 888 Meeeeeee ee 8-Meeeeeee-8-eeeee Meee Meeee Meeeee eeee Meeeee-8,8-eeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8,8-Mee(eeeeeeeeeeeee)-8-eeeeeeeeee-8-ee-8-eee (888):[‌888‌]

Me e eeee ee eeeee eeeee 888 (8.88e, 8.8888eee) ee eeeeeee (88eM) (MMMMMMM: eeeeeeeeee) ee e 88-eM eeeee eee eeeeee eeeee e eeee ee MeMM (8.888e, 8.8888eee) ee eeeeeee (88eM). M eeeeeeeee eeeeeeeeeee eeeeee eeee eeeeeeeeeeee ee eeeeeeeee 888; eeeee: 8.88e (88%). Meee eeeeeeeeeee eee eeeeeeeee eee eeeeeeeeeeeeee (MM8Me8/eeeeeee). Mee eeeeeeeee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeeee eee eeeeeeee eee eeeeeeeee (888°M/8.8Meee) ee eeeeeee eee eeeeeee 888; eeeee: 8.8e (88%).

8,8-Meeeeeeee-M,M,M,M-eeeeeeeeeee-8-eeeeeeeeee-8-eee-8,8-eeeeeee (888):[‌888‌]

Me e eeee ee eeeee eeeee 888 (8.88e, 8.8888eee) ee Me8M (88eM) eee eeeee e eeee ee MeMM (8e) ee Me8M (88eM), eee eee eeeeeee eee eeeeeee ee eeeee ee ee eee 8e. Mee eeeeeee eee eeeeee MeMM eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeeee eee eeeeeeee eee eeeeeeeee (8888°M/8.8Meee) ee eeeeeee eee eeeeeee; eeeee: 8.88e (88%).

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