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Please login or sign up for a free trial to access the full content. Variation 4: Conjugate Addition

DOI: 10.1055/sos-SD-007-00207

Oishi, M.Science of Synthesis, (20047294.

Noncatalyzed conjugate addition of triorganoaluminum compounds to simple enones is rather limited, but there are some successful examples of the conjugate additions using relatively nucleophilic aluminum reagents or activated alkene substrates. In contrast, transition-metal-catalyzed reactions are more general and useful in organic synthesis, and will be discussed in a later part of this section.

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Meeeee 88 Meeeeeeeeeeeeee Meeeeee Meeeeeee ee Meeeeeeeeeeeeeeee eee Meeeeeee-8-eeeee[‌888‌]

Meee eee Meeeee eeeeeeee eeee 8,8-eeeeeeee ee eeeeeee- eee eeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeee eeeeeee eeeeeee ee eeeeeeee e eeeeee eeeeeeeeeeee eeeee eeeee ee eeeeeee eeeee/eeeeeee eeeeeee eeee ee eeeeeeee ee eeeeeeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeee Meeeeeee ee Meeeeee- eee Meeeeeeeeeeeeee Meeeeeeee[‌888‌,‌888‌]

Meeeeee eeee eeeeeeeeeee eeeeeeeee eeeeeeeee 8,8-eeeeeeee ee eeeeee eeeeee, α,β-eeeeeee eeeeeeeee, eee α,β-eeeeeee eeeeeee, eeeeeeeeeeee eeeeee eeee eeeeeeeeee eee eee eeeeeeeeeee ee eeeeeeeeeee eeeeeeeeeeeeeee eee eee eee eeeeeeeee ee eee eeeeeeeee eeeeeeeeee ee eee Meeeeee eee eeeeeee eeee eee eeeee eeeee eeee.[‌888‌] Meeeee eeeeeeeee eee eeeeeeeeeee eeeeeee ee eeeeeeeeeeeeee eee eeeee eeeeeeeee, eeeeeeeeeeeeee eeeeeee- eee eeeeeeeeeeeeeee eeeeeeeee eeee eeee eeeeeeee eee eeeeeeeee eeeeeeee ee 8-eeeeeeeeeeeeeeee-8-eeeeee ee eeeeeeeee e eeeeeeeee ω-eeee eeeee (Meeeee 88).[‌888‌,‌888‌] Me eeeeeee, eeee eeee ee eeeee eeeeeeeee eee eeeeeee eeeeeeee eee eee eeeeee eeeeeeeeeeeee eeeeeeee eee eeeeeeee eee eee eeeeeeeeeeeeeee eeeeeeeee ee eee eeeeeeee eeeeeeee eeee ee eeeeeeeeeeeeeeee eee eeeeeeeeee eeeeeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeee ee Meeeeeeeeeeee Meeeeeeee[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeeeeeeee Meeeeeee ee Meeeeeee Meeee ee Meeeee[‌888‌]

Meeeeee, eee eeeeeeeeeeeeeeeeee-eeeeeeee 88, eeeee-eeeeeeeee eeeeeeee eeeee eeeee ee eeeeeee eee eeeeeee ee eee eeeeeeeee ee eeeee eeeee eeeeeeeeee eeeeeeeee eeeeee, eeeee eee ee eeeeeee eeeeeee eeee eeeeeeeeeeee eeeeeeee ee eeeeeeeee eee eeeeeeeeeeeee eeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 eeeee-Meeeeeeee Meeeeeeee Meeeeeee ee Meeeeeeeeeeeeee[‌888‌]

Meeeeeeeeeeeeee eee eeeeeeeee eee eeeeeeeeeeee eeeeee ee eee ee eeeeee eeeeee eeee ee eeeeeeeeeeeeeee eeee eeeeeeeee ee eee eeeeee-eeee eeeeeeee; eeee eee eeeeeee ee eee eeeeeeeee ee 88,88-eeeeeeeeeeeeeeeeeeeee.[‌888‌] Me ee eeeeeeeeee eeee eee eee eeeeeeeee eeeeeeeee eeee eeeee eeeeeee ee eeeeee 8,8-eeeeeee, eeeeeee eee eeeeeeeeeeeee eeeeeee eeeeeee­eeeeeeee eeeeeeeee eeeee eeee eeeeeeeeeeeeeee ee e 8,8-eeeeeee ee eeee eeeeeeeeeee. Me eeeeeeeee ee Meeeee 88, eeeeee eeeeeeeee eeeeeeeeee, e.e. α,β-eeeeeeeeeee eeeeeeee eeeeeee eeee eeeeeeeeee eeeeeeee-eeeeeeeeeee eeeeee eeee ee eeeeeeee eee eeeee ee eee α-eeeeeeee, eeee eeeeeeee eeee eeeeeeeeeeeeee eeeeeeeee eee eeeeeeeeee eeeeeeeeeeeeeee 8,8-eeeeeeee eeeee eeee eeeeeeeeee.[‌888‌‌888‌] Me eee eeeeeeeee eeeeeeeee eee eee eeee eeeeeeeeeeeeeee, eeeeeeeeeeeee eee eeeeee eeeeee eeee eeeeeeee ee eeeee ee eeeeeeeee eeeeee eee eeeeee eeeeeeeeeeeeee eeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeee Meeeeeeee Meeeeeee ee Meeeeeeee Meeeeeeeee[‌888‌,‌888‌]

8-Meeeeeeeeeee eeee eeee eeeeee ee ee eeeeeeeeeee Meeeeee eeeeeeeee eeeeee eeeeeeeeeeeeee eeeeeeeee, eeeee eeeeeeeeeeeeeee, Meeeeeee eeeeeeee, eee eeeeeeeeeeee eeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeee eeeeee eeeee ee eeee eeeeeeeeee eee eeeeeeee.[‌888‌,‌888‌] Mee eeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeee ee eeeee eeeee eeeeeeeee eeee eeeeee eee eeeeeee 8-eeeeeeeeeeee eeeeeeee ee eeeeee ee 8°M ee 88°M, eeeeeeeeeeee, eeeeee eeee ee eeeee eeeeeeeee (e.e., 88) ee eeeeee eeeeeeee (e.e., 88), eeeeeeeee ee eee eeeeee eeeeeeeeee (Meeeee 88). Mee eeeeee eee eeeeeee ee eee eeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeee, e.e. eeeeeeeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeee Meeeeeee ee Meeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeee eeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeee ee eeeeee eeeeee, eeeeee [(8-eeeeeeeeeeeee)eeeeee]eeeeeee 88, eee eeee eeeeeee. Meeeee eeeeeeeeeeeeeeeeee eeeeeeeee eeeeeeee ee 88 eee eeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeeee ee eee eeeeeeee eeeeeeeeeeee (e.e., Meeeee 88).[‌888‌,‌888‌] Meeeeeeee ee eee eeeeeeee eeeeeeeeeee eee eeeeeeeeeeeee eeeeeeeeeeee (MM8 eeeee), eeee eeeeeee eee eeeeeeee eeeeee ee eeeeeeee ee e eeeeeeeee eeeeee ee eee eeeeeeee eeeeeeee eeee eeeee ee ee eeeeeeeee ee eeeeee eeee eeeeee eee eeeeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeeee Meeeeeeee Meeeeeee ee [(8-Meeeeeeeeeeee)eeeeee]eeeeeee[‌888‌,‌888‌]

Meeeeeeeeeeeee-eeeeeeee eeeeeee eeeeeeee ee eeeeee, ee eeeeeeeeee eeeeeeeee eee eeeeeeeeee eeeeeeee eeeeee, eee eeee eeeeeeeeeee eeeeeee ee Meeeee eee ee-eeeeeee.[‌888‌‌888‌] Meee eeeeeeee eee eeeeeee eeeeeee: eeeeeeeeeeeeeeeeeeeeeeee eeeeeee eee eeeeeeeeeeeeeee eeeeeee. Mee eeeeeeeeeeeeee ee eeeeeeee ee eeeeeeeee eeeeeee eeeee ee eeeeee eeeee eeeeeee[‌888‌] eee eeeeeeeee eeeeeeeeeeeeeee eeeeeeee[‌888‌] ee eeeee ee eeeeeeeeee, eeeeeeeeeeeeeeeee, eee eeeee eeeeeeee. Me eeeeeee, eee eeeeee eeeeeee, e.e. e eeeeeeeeeee ee eeeeeeeeeeeeeeee eee eeeeeeee eeeeeee, eeeeeeee eeeeeeeeeee eeeeeeeeee 8,8-eeeeeee, eeeeeee eee eeeeee eee, eeeeeeee eeee eee eeeeee eeeeeee eeeeeeeeee ee eeeeeeee ee eeeeeee ee eeee eeeeeeeeeee eeeeeeeee,[‌888‌] eeeee eeeeeeeeeeeeeeeee eeee eeeeee eeeeeeee. Meeeeeee eeeeeeee ee eee eeeeeeeeeeeeee eee eeeeeeeeee ee Meeee 8 eee Meeeee 88. Mee eeeeeee ee eeeeeeeeee ee eeeeeeeee eeeeeeeeeeeeee ee eeeeee,[‌888‌,‌888‌] eeeeeeee,[‌888‌] α,β-eeeeeeeeeee eeeeeeeeee eeee eeeeeeeeeee,[‌888‌] eee eeeeeeeeeeeeeeee.[‌888‌]

Meeee 8 Meeeeeeeeeeeee ee Meeeee[‌888‌]

Meeee Meeeeee Meeeeee Meeeeeeeee Meeee (%) Mee
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MMM, Me8Me MMM, 88°M, 8e 88 88 [‌888‌]
Me8MeMM eeeeeee, 88°M, 8eee 88 88 [‌888‌]
MMM, Me8Me MMM, ee, 88e 8 88 [‌888‌]
Me8MeMM eeeeeee/eeeeeee, 8°M, 8.8e 8 88 [‌888‌]
MMM, Me8Me Me8M, 88°M, 88e 88 [‌888‌]
Me8MeMM eeeeeee/eeeeee, 88°M, 8e 88 [‌888‌]
MMM, Me8Me MMM, ee, 8.8e 88 [‌888‌]

Meeeee 88 Meeeeeeeeeeeee ee Meeeeee Meeeeeeeee Meeeeeeeee[‌888‌,‌888‌,‌888‌]

Meeeeee eeeeeee eeeeeeeee eeee eee eeeeeeeee ee eee eeeeee ee eeeeeeeeeeeeeeee eee eeeeeeee eeeeeee ee eeeeeeeeeeeeeee eeeeeeee ee eeeeeee 8,8-eeeeeeee eee-eeeeeeeee, eee eeee e eeee-eeeeeeeeeee eeeeee ee eee eeeeee eeeeeee ee eee β-eeeeee eeeee 8,8-eeeeeee.[‌888‌] Meeeeeee eeeeeeee eeeeeeeee eeee eeeeeeeeeeeeeee eeeeeee eee ee eeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeeeeeee ee eeeeeee eeeee eeee eeeeee ee eeee ee eeeeeeeee eeeeee.[‌888‌] Meeeeeeee 8,8-eeeeeeeeee eeeeeeeee ee eeeeeeeee eeeeeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeee ee eeeeee 8,8-eeeeeeeeeeeeeee eee eeee eeeeeeee (Meeeee 88).[‌888‌] Mee eeeeeeee eeee ee eeeeeeeeeeeeeee ee eeeeeeeee ee eee eeeeeeeeeee eee eee eeeeeeeeeeeeeeeeeeeeee eee eeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeeee. Meeee eeeeee eeeeeeeee ee eee eeeeeeee, eeeeeeeeeee eeeeeeee eeeee eeee eeeeeeee eeeeeee eeeeeeeeeeee.

Meeeee 88 Meeeeeeeee Meeeeee Meeeeeee ee 8,8-Meeeeeeeeeeeeee[‌888‌]

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Meeeee 88 Meeeeee MeeeeeeeeMeeeeeeee Meeeeeee ee Meeeee[‌888‌,‌888‌]

Meeeeeeee eeeeeee ee eee eeeeee eeeeeee eeeeeeee ee eeeeeee. Meeeeee, 88eee% ee MeMM8MeMe eee eeeeee ee eeeeeeee eee 8,8-eeeeeeee (Meeeee 88).[‌888‌] M eeeeeeee eeeeee ee eeeeeee eeeeeeeeee eeeeee ee eee eeeeee ee eeeeeeeeeee ee eeeeeeeeeeee eee eeeeeeee.

Meeeee 88 Meeeeeeee Meeeee(M)-Meeeeee Meeeeeeee Meeeeeee[‌888‌]

Me eee eeeee eeee eeeeee(M) eeeeeee eeeeeeeee 8,8-eeeeeeee ee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeee ee eeeeeeeeeeeeeee ee eeeeeee eeeeeeeeeeee.[‌888‌,‌888‌] Meeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeeeeee, eeeeeeeeeeeeeeee, eeeeeeeeeeeeeeeee, eee eeeeeeeeeee­eeeeeeee eee ee eeeeee eee eeeeeee eeeeee ee eeee eeeeee eeeee eee ee eee eeeeeeeeeeeee eeeeeee eeeeeeee ee eeeeeeeeeeeeeeee eeeeeeeee eeeee ee eeeeeeeee eeeeeeee eeeeee (Meeeee 88).

Meeeee 88 Meeeee-Meeeeeeee 8,8-Meeeeeee ee Meeeeeeeeeeeeeee Meeeeeeee ee Meeeee[‌888‌,‌888‌]

Meeeeeeeeee 88

M8 Meeeeee eee M88Me Meeee (%) Mee
Me eeee 88 [‌888‌,‌888‌]
Me eeee 88 [‌888‌]
Me eeeeeee 88 [‌888‌]
Me eeee 88 [‌888‌]
eMe eeee 88 [‌888‌]
eMe eeeeeee 88 [‌888‌]

Meeeeeeeee eeeee eeeeeeeeeeeeeee,[‌888‌‌888‌] eee eeeeeeee ee eeeeeeeeeeeeeeeeeeeee eeeeeeeeee eeeeeeee eee eeeeeeee eeeee eee eee eeeeee eee eeeeeeee eeeeeee ee 8.8eee%.[‌888‌] Meeeeeee ee α,β-eeeeeeeeeee eeeeeeeee eee eeee eeeeeeee eeeee eee eeeeeeeee eeeeeeeeee.[‌888‌,‌888‌] Meeeeeeeeeeeeee ee eee eeeeeee ee eeeeee ee eeee eeeeeee eeeeeee ee eeeee eeeeeeee, eeeee eeeeee eee eeeeeee eeeee eeeeeeeeee eeeeeeeeeeee 8,8-eeeeeeee ee eeeee eeeeeee eeeeeeee. Me eeee eeee, eeeeeeee ee eeeeeeeeeeeeeeeeeeeee eeee eee eeee eeeeeeee eeeee.

Me eeeeeeeeeeeeeeee eeeeeee ee eee eeeeee-eeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeee eeeeeeeee eeeeeee eeeeeee. Meee eeeeeeee eeeeeeeeeeeeeeeeeeee eee eeeeeeee, ee eeeee ee Meeeee 88 (e.e., eeeee eeeeee eeeeeee 88 eee 88).[‌888‌,‌888‌] Meeeeee, eee eeeeee eeeeee eeeeeeee eee eeeeeee ee e eeeeeeeeeeeeeeeeee eeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeee eee eee eeeeeeeee ee eeeeeeeeeeee (88M) eee 88-eeeeeeeeeeeeeee (88M).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeee Meeeeeeee Meeeeeee ee Meeeeeeeeeeeeeee Meeeeeeee ee Meeeee Meeeeeeee ee Meeeee Meeeee Meeeeeeee[‌888‌‌888‌]

Meeeee-eeeeeeeee eeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeee eee eeeeeeeeee eeeeee eee eee ee eeeeee eeeeeeeee.[‌888‌,‌888‌] Meeeeeeee eee eeeeeeeeeeeeeeeeeee ee M- eee M-eeeeeeee eeeeeeee, e.e. 88, eeee eeeeeee eeeee e eeeeee eeeeeeee.[‌888‌] Meeee eeeeee eeeeeeeee, eee(eeeeee­eeeeeeeee)eeeeee(MM) eeeeeeee eeee eeeeeeee ee eeeeeee, eee eeeee eeeeeeeee eeeeeee ee eeee eeeeee eeeee eeee eeeeeeeeee (Meeeee 88). Meeeeee eeeeeeeeeeeeeeeee, eeeeeee eeeee­eeee­eeeeeeeeeee eee eeee ee eeee, eee eeeeeeeeeeeee eeeeeeeee eee eeeeeeee eeee.[‌888‌]

Meeeee 88 Meeeee-Meeeeeeee 8,8-Meeeeeeeeee ee Meeeee[‌888‌,‌888‌]

Meeeeee eeeeee eee eeeeee eeeeeee eee eeeeee eeeeeeeee eee ee eee eeeeeee eeeeeeeee eeeeeeee. Me eee eeeee eeee, eee(eeeeeeeeeeeeeee)eeeeee(MM)eeeeeeeeeeeeeeeeee eeeeeee eeeeeeeee eeeeeee eeeee eeeeeeee eeee eeeeeee(eeeeeee)eeeeeeee eeeeeeeee ee e eeeeeee ee eeeeee (Meeeee 88).[‌888‌,‌888‌] Mee eeeeeeeee eeeeeeee eeeee ee ee eeeeeee ee eeeeeeeeeeeee eeeeeeeee eeeeeee e β-eeeeeeee.[‌888‌] Mee eeeeeee, eeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeeee eeee eeeeeeeeeeeeee eeeeeee eeeeeeee.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeee Meeeeeee ee Meeeeeeeeeeeee-Meeeeeeeeee Meeeeee ee Meeeee[‌888‌,‌888‌]

Me eeeeeeee ee eeeeee eee eeeeeee eeeeeeee, eeeeeee(eeee)eeeeeeee eeeeeeeee eee eeeee eeee eeee eeeeeeeeee eeeeeeee eeeeee eeee ee eee eeeeeee 88 ee eeeeee eee β-eeee eeeeee 88 (Meeeee 88).[‌888‌] Me eeeeeeee, eeeeeeeeeeeeeee ee eee eeee eeeeeee, eeeeeeeeee 8,8-eeeeeeee, eee eeeeee eeeeee ee eee eeeeeeeeee eee eeeeeeeee.

Meeeee 88 Mee(eeeeeeeeeeeeeee)eeeeee(MM)-Meeeeeeee 8,8-Meeeeeeee ee Meeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

(8α,8α,88β)-8-Mee-8-eeeeeeeeeeeeeee-88-ee Meeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

M 8M eeee ee MeMeMe (88eeee) ee MMM eee eeeee ee e 8M eeeeee eeee ee Me8MeMe (88eeee) ee 88°M. Mee eeeeeee eee eeeeeee eee 88eee ee 88°M. Meee e eeee ee eeeee 88 (8.8e, 88eeee) ee MMM (88eM) eee eeeee ee 88°M, eeeeeeee ee Me(eeee)8 (888ee, 8.8eeee). Mee eeeeeee eee eeeeeee ee 8°M eee 8e, eeee eeeeeeee eeee ee MM8Me eee eeeeeee eee 88eee. Mee eeeeeee eee eeeeeeeee (MeMMe) eee eeeee (Me8MM8). Meeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee) eeee 88 ee eeeeeeeee eeeeeeee; eeeee: 8.8e (88%); ee 888°M.