Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest. Please login or sign up for a free trial to access the full content.
20.2.1.8.5.2 Variation 2: Homologation by Multiple Carbon Atoms

DOI: 10.1055/sos-SD-020-00203

Vedantham, P.; Jiménez, M.; Hanson, P. R.Science of Synthesis, (200720279.

Carboxylic acids can be homologated by more than one carbon using metal-catalyzed processes. In general the homologation products may be formed by reaction of a carboxylic acid with an allene, catalyzed by either a rhodium or copper species. For example, allene reacts with but-3-enoic acid at 85°C, using catalytic amounts of chlorotris(triphenylphosphine)rhodium(I), and two possible products are formed in 23% yield. These are a 3,5-dienoic acid 48 and a 3,6-dienoic acid 49, and this mixture is attributed to the ability of the allene to form either an allylic or vinylic system with the metal (Scheme 19).[‌39‌]

Meeeee 88 Meeee-Meeeeeeee Meeeeeeeeeee ee Meeee Meeee Meeeeee[‌88‌]

Meee eeeee eeeeeee eee eeeeeee eeee eee-8-eeeee eeee eeeee eee eeee eeeeeeeeee eee eeeeee eeeeeeee ee ee eeee, eeee eee eeeeeee eeeee 88% ee eee eeeeeeee ee 8-eeeeeeeeee-8,8-eeeee. Me eeee eeee, eeee 8,8- eee 8,8-eeeeeee eeeee eee eeeeeeee, eeee eee 8,8-eeeeeee eeeee eeeee eeeeeeeeeee. Me eee eeee eeeee eeee eee eeeeeee eeeeeee ee eeeeeeee ee eee eeeeee ee eeeeeee ee eee eeeee eeeeeeee. Mee eeeeeee, eeeeeeeee ee eee eeeeeee eeeee ee eeeeeeee eeee eeee-8,8-eeeee eeeeeeeee eeeeeeee eeee eee-8-eeeee eeee ee eee eeeeeeee ee eeeeeeeee(eeeeeeeeeeeeee)eeeeeee(M) eee e eeeeeee ee eeeeeeeeee-eeeeeeeeee eeeeeee ee 88°M eeee 8eeeee (Meeeee 88). Mee eeeee ee 8,8-eeeeeee eeee 88 eee 8,8-eeeeeee eeee 88 eeeeeee eeeeeeeeeeee eeee eeeeeeeeee eee eeeeeeeeee ee eeeeeee, eee eeeeeee eeeeeeeeeeeeeeeeee eeeee e eeeee ee 88:88, eeee eeeeeee ee 8:88 eee eeeeeeeeeeee eeeeeeeee.

Meeeee 88 Meeeee Meeeeee ee Meeee-Meeeeeeee Meeeeeeeeeee ee Meeee Meeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (88/88) Meeee (%) Mee
Me 88:88 88 [‌88‌]
MeMe 8:88 88 [‌88‌]
MMe 8:88 88 [‌88‌]
Me 88:88 88 [‌88‌]

Mee eeeeeeeee ee eeeeeee eeeee 88 eee eeee eeeeeeeeeeee ee e eee-eeee eeeeeee. Meeeeee, eee eeeeeeee eeeeeeee eeee 88 ee eeeeeeeeeee, ee eeee ee eeee eeeee (8888%), ee eeeeeeee ee e eeeee-eeeeeeeeeee eeeeeeeeee eeee 88 eeee e eeeeeee eeeeeeeeeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeeeee. Mee eeeeeeee eeeee eee eeee eeeeeee eeee e eeeeeeee 8-eeeeeeeeee, eeeeeee ee 8-eeeeeeeeee, e.e. 88 (e=8, 8, 88, 8888), eeeee e MeeeeeMeeeeeeeeee eeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee Meeeeee Meeee eee e Meeeee-Meeeeeeee Meeeeeeeeeeeee Meeeeeee[‌88‌]

Meeeeeeeee eeeee eee eeee ee eeeeeeeeeee ee eee eeeeeeee ee eee eeeeeeeee Meeeeeee eeeeeeee (eee eeeeeee 88 eee 88), ee eee eeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeee(MM) ee eeeeeeeeeeeeeee, ee eeee eee eeee-eeeee eeee 88 ee 88888% eeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee ω-Meeeeeeeee Meeee eee Meeeeeee ee Meeeeeee Meeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeee Meeee 88 eee 88; Meeeeee Meeeeeeee:[‌88‌]

Mee Me eeeeeeee, eee-8-eeeee eeee, eee eeeeee, ee e 8:88888:88888 eeeee eeeee, eeee eeeeee ee e eeeee eeeeeeeee eeee ee eeeeeeeee eeeeeee eeeeeeeeeee ee eeeeeeee eee eeeeee ee ee eee eeee ee 88°M eeee eeeeeeeeee eeeeeeee. Mee eeeeeee eeeeeeee eee eeeeeeeee ee eeeeeeeeeeee eeeeeeee eeeeeeeee, ee eeeeeee eee eeeeeeeee eeeee.

Mee-8-eeeee Meee (88, e=8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeee ee e eeeeeee eeeeeeeeeeeeeeeeeeeeeeee eeeeeee (8.88e, 88eeee) ee eee MMMM (88eM) eee eeeee eeeeee, eeee e eeeeee ee 88eee ee 8°M, e eeee ee 8-eeeeeeeeeeeee eeee (88, e=8; 8.8e, 88eeee) ee MMMM (88eM). Meeee eee eeeeeeee eee eeeeeeee, eee eeeeeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 8e. Mee eeeeeee eee eeeeeeee ee 888°M eeee M8M (88eM), eeeeeeee ee eeeeeeeeeeeee eeee 88% MMe. Mee eeeeeee eee eeeeeeeee eeee eeeeee eee eee eeeeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eee eee eeeee eeeeeeee eee eeeeeeeee (ee 8888°M/8.8Meee) ee eeeeee 88 (e=8); eeeee: 8.8e (88%).

Meeeeee-88,88-eeeeeee Meee (88, e=88; e=8); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeee-88-eee eeee (88, e=88; 8.8e, 8.8eeee) eee eeeeeeeee ee ee ee MMM eeee (8.8 eeeee). M eeee ee MeMe (8.88 eeeee) ee 88% ee MeMM8 eee eeeee eeeeeeee ee MM8MMMMe (8ee ee eeeeeeee). Me eeee (eeeeee) eeee eee eeeee, ee eeeee eeeeeeee, eee 8-eeeeeeeeee (88, e=8; 8.88e, 8.8eeee) eeeeeeeee ee MeMM/Me8M (8:8, 88eM). Me eeeeeeee ee 88 eee eeeeeee eeeeee eeee, eee eeee eeeeee eeeee ee eeeeeeee ee e eee eeeee ee e 88% ee MM8MMMMe eeee. Meeee eeeee, eeeeeeee eeeee eee ee 88 eee eeeeeee, eeee eeeeeeee eeeeeeeee ee 88eee. Mee eeeeeee eee eeee eeeeeeeee eeee 88% MMe eee eeeeeeeee eeee Me8M. Mee eeeee eeee 88 (e=88; e=8) eeeeeeee eeee eee Me8M eeeeeee eee eeeeeeeeeeeeee (eeeeeee) eee eeeee eeeeeeeeeeeee.

Meeeeeeeee Meee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee 88 ee MMM eee eeeee e 8.8M eeee ee Me8MeMe8 ee MMM (8eM, 8.8eeee)[‌88‌] ee 88°M. Mee eeeeeee eee eeeeeee eeeeee ee 88°M eee eeeeeee eeeeeeeeee eeeee e eeee ee 88 eee eeeee eeee e eeeeee ee 88eee. Meeee 8.8e ee eeeeeeee ee 88°M, eee eeee e eeeeeee 8e ee eeeeeeee ee 88°M, 88% M8MM8 (888eM) eee eeeee ee eee eeee eeee eeeeeee, eeeeeeeeee eee eeeee eeeee eeee eee eeeeeee. Mee eeeeeee eee eeee eeeeeeeee eeee eeeeeee (8 × 888eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee 8% M8MM8, eeeee (MeMM8), eee eeeee eeeeeeeee ee eeee 88; eeeee: 8888e (88888%); ee 8888°M. Meeeeeeeeeeeeeeee eeee e eeeeee eeee eeeeee eeee ee MMMM eee eeee eeeeee eeee eeee 88 ee eeeee eeeeeeeee (88eee% eeeeee ee eeeeeeeeeeee eeeeeeee eeeeeeeeeee; ee 8888°M). Meeeee ee eeee eeeeee (8.8Meee) eeee 88 eeee eeee eeeeeee eeeeee (88eee% ee eeeeeeeeeeee eeeeeeee eeeeeeeeeee; ee 88.8°M).

References