Science of Synthesis

Roy, K.-M., Science of Synthesis, (2010) 47, 1141.

Cross-coupling reactions of vinylaluminum compounds with allylic derivatives parallel the corresponding reactions using organoboron compounds (see Section ‌47.3.1.1.2.2‌). Thus, several isomerically pure E-1,4-dienes ‌19‌ are obtained in good yields by hydroalumination of alkynes ‌18‌ and subsequent allylation of the intermediate vinylaluminum compounds in the presence of a copper(I) catalyst (‌Scheme 12‌).[‌30‌] In a similar approach, the use of palladium catalysts in conjunction with carboalumination of alkynes provides a stereo- and regioselective synthesis of trienes ‌21‌[‌31‌] and tetraenes ‌22‌[‌32‌] by coupling of the vinylaluminum compounds ‌20‌ with geranyl or the isomeric neryl derivatives (‌Scheme 13‌).

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‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeeee Meeeeee eee Meeeeeeee[‌88‌,‌88‌]

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‌Meeeee 88‌ Meeeeeeeee ee Meeeeee eeee Meeeeeeeeee Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeeeeeeeeeeeee-8,8-eeeee (‌88‌, M8 = Me; M8 = M); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eee eeeeeeeee ‌88‌ (M8 = Me; M8 = M; 8.8 e, 88 eeee) ee eeeeee (88 eM) eeeee e eeeeee eeeeeeee ee M8 eee eeeee MMMMM-M (8.8 eM, 88 eeee), eeeee eeeeeeeeeee eee eeeeeeeeeee ee 88–88°M ee eeeee ee e eeeee eeee. Meeee eeeeeeee ee ee eee 88 eee eee eeee ee 88°M eee 8 e, eee eeeeeee eee eeeeee ee ee. M eeee ee eeeee eeeeeee (8.8 e, 88 eeee) ee eeeeee (88 eM) eee eee MeMe (8.8 e, 88 eeee) eeee eeeee ee eeee, eeeeeeeeeee eee eeeeeeeeeee ee 88–88°M. Mee eeeeeee eee eeee ee ee eee ee eeeeeeeeee 8 e eee eeee eeeeee eeee eeeeee (MMMMMMM: eeeeeeeeee eeeeeeee) eeee 88% M8MM8 (888 eM) eeeeee ee e eeeee ee eeeeeeee eee eeee ee e MMe8 (MMMMMMM: eeeee)/eee eee eeee. Meeee eeeeeeeeee eeeeeee Meeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eeeee eee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee eeeeeee. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee ee Me8MM8 eee eeeee (MeMM8). Meeeeee ee eee eeeeeeee eee eeeeeeeeeeee eeeeeee e eeeee Meeeeee eeeeee eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M/8 Meee.

α-Meeeeeeee [(M)-‌88‌]; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

Me e eeee ee Me8Me (8.88 e, 8.88 eM, 88 eeee) eee Me(Me)8Me8 (8.88 e, 8 eeee) ee 8,8-eeeeeeeeeeeeee (88 eM) eee eeeee ee ee eeeee M8 eee-8-ee-8-eee (8.88 e, 88 eeee) ee eeeeee. Mee eeeeeee eee eeeeeee ee ee eee 88 e, eee eeee eeeeeee eeeeeeee (8.88 e, 88 eeee), Me(MMe8)8 (8.88 e, 8 eeee), eee MMM (88 eM) eeee eeeee. Meeee eeeeeeee ee ee eee 8 e, eee eeeeeee eee eeeeeee eeee M8M (88 eM) eee eeeeeeeee eeee eeeeeeee. Mee eeeeeee eeeeeeee eeee eeeeee eeee ee MeMMM8 eee eeeee (MeMM8). Meeeeeeeee, eeeeeee ee eee eeeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeeeeeeee eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M/8.88 Meee.

8-Meeeeeeeeee-8,8-eeeee (‌88‌, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eee eeeeeeeeeee eeeeeeee, eeeeeeee ee eeeeee Me eeeeee (8.888 e, 8.8 eeee) eeee eeeee eeeeee (8.88 eM, 8.8 eeee) ee MMM (8.8 eM) ee ee eee 8 e, eee eeeee eeeeeeeeeeeeeee (8.88 eM, 8.8 eeee) ee ee. Mee eeeeeee eee eeeeee ee 88°M eee eeeeeee eee 8 e. Meeee eeeeeeeee eeee eee MMe (88% e/e, 8.8 eM) ee ee, eee eeeeeee eee eeeeeeeee eeee Me8M, eee eee eeee eee eeeeee eeee eeeee eee eeeee (MeMM8). Meeeeee ee eee eeeeeeee eeeee eeeeeee eeeeeeee eee eeeeeeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee) eeee eee eeeeeee; eeeee: 8.888 e (88%).

References