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Please login or sign up for a free trial to access the full content. Method 6: By Addition of Organocopper Reagents

DOI: 10.1055/sos-SD-026-00382

Plaquevent, J.-C.; Cahard, D.; Guillen, F.Science of Synthesis, (200526525.

Although organocopper reagents can undergo 1,2-addition onto ketones,[‌73‌] this reaction is usually far slower than 1,4-addition onto enones. Since the initial research in this area,[‌74‌] various types of organocopper reagents have been used; here, only stoichiometric use of copper is discussed (catalytic use of a copper salt or complex with a stoichiometric amount of another organometallic, for example organozinc and Grignard reagents, is discussed in Sections and Several types of organometallic reagents that can be classified according to the valency of copper are available for 1,4-addition. Valuable information on the preparation and use of organocopper reagents, including detailed experimental procedures, has been described.[‌75‌]

Meeeeeeeeeeeeeee eeeeeeee (M8Me) eee eeeeeeeee ee eeeeeeee ee 8 eeeeeeeeee ee ee eeeeeeeeeeeee ee Meeeeeee eeeeeee eeee e eeeeee eeeeee ee ee eeeeeeeee eeeeeeee ee ee eeeeeee eeeeee eeee eeeeeeeee eeeeeeeeee eeeeee.[‌88‌] Mee eeeeee eeeeee eeeee eeeeee ee eeeeeeeeeeeeeeee eeeeeee eeeeeee eeeeeeeeee eeeeee eeee eee eee eeeeeeeeee eeee eeeeeeeeeeeee ee Meeeeeee eeeeeeee, eeee ee eeeeee, eeeeeeee, eeeeeee, eeeeeee, eee eeeeeeee. Mee ­eeeeeeeeee ee eeeeeeeeeeeeeeee eeeeeeee eeeeee eeeeee ee eeeeee eee [eeee-eeee eeeeeeeeeeeeeeee eeeeeeee eee eeeeee eeeeeeeeee, eee eeeeee eeeeeee eeeee e eeeeeee (M8MeM)]: eeeeeee, eee eee ee eeeeeeeeeeeeeeeeeeeee[‌88‌] ee e Meeee eeee (e.e., MM8MMe8 ee MeMe8)[‌88‌] eeeeeee eeeeee eeeeeeee ee eeeeeeeeeeeeeeee ee eeeeee (e.e., eeeeeee 88 eeee eeeeee 88, Meeeee 88).

Meeeee 88 Meeee Meee Meeeeeee Meeeeeeee Meeeeeee ee Meeeee[‌88‌]

Meeeeeeeeeeee eeeeeeee (eeeeeee M88MeMe ee M88MeMeM) eeee eeeeeee eeeeeeee eeeeeeeeeeeeeee, eeeeeeeee, eee eeeeeeeeee eeee eeee eeeeeeee eeee eeeeeeee ee 8,8-eeeeeeee ee eeeeee. Meee eee eeeeeeeeeeee eeeeeeee ee eeeeeeee ee 8 eeeeeeeeeee ee ee eeeeeeeeeeeee ee Meeeeeee eeeeeee ee e eeeeee eeeeee. Meeeeee eeee eee M8 eeeee ee eeeeeeeee, eee eeeeeeeee eeeeeeeeeeeeeeee eeeeeee eeeee eeee eeeeeeee. Me eeeee ee eeeeeee eeee, eeeee eeeeeeeeeeeeee (M8M8MeM, eeeee M8 ee eee eeeeeee eeeeeeeeeeee eeeee eee M8 e eeee eeeeee eeeeeeeeeee eeeee) eeee eeee eeeeeee. Meeeeeeeeee M8 eee ee ee eeeeeee, (eeeeeeeeeeeeee)eeeeee (ee eeeeeee eeeeeee), eeeeeee, ee eeeeeee eeeee. M eeeeeee eeeeee eeeeeeee ee eee eee ee eeeeeeeeeeeee eeeeeeee [M8Me(M)M, eeeee M ee e eeeeeeeeeeeeeee ee eeeee eeeeee, eeeeeee MM, MMe, Me-Me, MMe8, e-Me, ee MMe8]. Meeeeeee eeeeeeeeeeeeee eee eeeeeee eeee eeeeeeee eeee eeeee eeeeeeeeeeee, eeeee eeeeeeee eeeeeeeee, eeee ee eeeeeeeeeee eeee eeeeeeeeeee eeeeee(M) eeeeeee (eee eeeeeeeeeeee), eee eee eeeeeeeeeee ee eeeeee eeeeeeeeeeeeee eeeeeee eee eeeee eeeeeeeee eee. Meeeeeee, eee eee ee eeeeeeeeee eeeeeeee eeeeee eee eeeeeeeeeee ee eeeeee eeeeeeeeeeeeee eeeeeeeeeeeeeeeee eeeeeeee. Meeeee eeeee eeeeeeeeeeeee, eeeeee eeeeee eeee eeeeee(M) eeeeeee eee 8 eeeeeeeeeee ee ee eeeeeeeeeeeee eeeeeee, eeeeeee eee eeeeeeeee ee eeeeeeeeeeeeee eeee eee eeeeeeeeee ee eeeeeeeeeeee. Me eeeeeeee, eeeeee(M) eeeeeee ee eeeeeeeeeee, eeeeeeeeeeeeee, eee eeeee-eeeeeeeeeee, eee ee eeeeee ee eee eeee eeeeee(M) eeeeeee. Meeee eeeeee eeeee eeeeeeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeee eeeeee eeee eeee eeee eeeeeee ee eeeee ee eeeeeee eee eeee ee eeeeeeee eeeeeeeeeeee M8 eeeeee.[‌88‌]

Meeeeeeeeeeeeeeeeeeee ee eeeeee eeee ee ee eeeeeeee ee eee eeeeeeeee eeeeeeee ee eeeeeeeeeeee ee eeeeee; ee eeeeeeee ee eeeeeeee eee eeeeeeeeeeee eeeeeee, ee eeee ee e Meeee eeee. Mee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeeeee ee eee eeeeeeeee eeeeeee, ee eeeeeeee ee eeeeeeee eeeeeeeeee, eeeeeeee eeeeeeeeeeeee ee eee eeeeeeeeeeeeee eeeeeee ee eee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeeeeeeee-Meeeeeee 8,8-Meeeeeee ee Meeeeeeeeeee Meeeeeee ee Meeeee[‌88‌]

Meeeee eeeeeeeeee eee eeeeeee eeeeeeeeee ee eeeeeeeeeee eeeeeeeeeeee eeeeeee. Meeeeee, eee eee ee eeeeeeeeeeeeeeeeeee eee eeeeeee eeeeee eeeeee eee 8,8-eeeeeeee ee eee eeeeeee eeeee eeee ee eeeee (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeeeeeeeeee 88 eee (8M)-8-eeee­eeeeee-8-ee-8-eee (88, M8=Me; M8=MMe, eeeee ee eeeee ee eeeeee ee e-eeeee eeeeeeeeeeeee) eeeeeeee eeee, eeeeeee eeeeeee eeeeeeeee, eeeeeeee eeeeee ee ee e-eee eeeeeeeeeeeee, eeee eeee eeeeeee. Meeeeeeeeeeeeeeeeee eeeeee eeeeeeee eeeeeeeee ee eeee eeeeeeee; eeeee eeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeee eeeeeee eeee ee eeeeeeeeee. Meeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee eeee eeeee eeee ee eee eeeeeeee ee eeeeeee eeeeee, eeeeeeeeee eeeeeeee ee eeee eeeeeeeeeeeeeeeeeee eeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeeeeee-Meeeeeee Meeeeeee ee Meeeee Meeeeeeeee ee Meeeee[‌88‌]

Meeee Meeee eeeee (eeee ee MM8MMe8 ee MeMe8) eee eeee ee eeee ee eeeeeee eeeeeeeee eeeeeeeee 8,8-eeeeeeee ee eeeeeeeeeeeeeeee eeeeeeee (Meeeee 88).[‌88‌] Me eeee eeeeeeeee e-eee eeeeee eee eeeeeee, eeeeeeeeee eeeeeee ee e eeeeee eeeeeeeeee eeeee eeeeeeeee eeeeeeeee ee eee eeeeeeee eeeee ee eee Meeee eeee.[‌88‌,‌88‌] Meeeeee eeeeeeeeeeee eeeeeee ee eee eeeeee eeee ee eee α- eee β-eeeeeeeee, eee β,β-eeeeeeeeeeeeee eeeee ee eeeeeeee 8,8-eeeeeeee (eeeeee eeeeeee 88) eeeeeee α-eeeeeeeeeeee eeeeee 8,8-eeeeeeee (eeeeee eeeeee 88).

Meeeee 88 Meeee Meeeeeeeeee Meeeeeee 8,8-Meeeeeee ee Meeeeeeeeeee Meeeeeee ee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (%) Mee
88 88
Me M M Me 88 [‌88‌]
Me M M Me 88 [‌88‌]
Me M Me Me 88 88 [‌88‌]
Me Me Me Me 88 8 [‌88‌]
(MM8)8 M Me 88 [‌88‌]

Meeeeeee ee 8-eeeeeeeeeee eeeeeeeeeee eeeeeeee eeeeee eee eeeee eeeee ee α/γ-eeeeeeeeeee.[‌88‌] Mee eeeeeeeeeeeeeee 88 (e=8), eeeeee (e.e., eee-8-eeeeeeeeee) ee eeeeee (e.e., 8-eeeeeeeee-8-eeeeeeeeee) eeeeeeeeeeee eeeeeeeeeeeeee eeeeee eeeeeee eeeee γ-eeee eeeeee eeeeeee 88, eeeeeee eee eeeeeeeeeeeeee 88 (e=8) eeee eeee ee eeeee eeeeee eeeeeee eee α-eeeeeeee eeeeee eeeeeee 88 (Meeeee 88). Me eeeeeeee, eeeeeeee ee eeeeee eeeeeeeeee eeeeee eee eeeeeeeeeee eeee γ ee α.

Meeeee 88 Meeeeeee ee Meeeeeeeeee Meeeeeee ee Meeeee Meeeee[‌88‌]

Meeeeeeeeee 88

e M8 M8 M8 M8 Meeee Meeee (%) α/γ-Meeeeeeeeee, 88/88 (M/M) Mee
8 M M Me M 88 8:88.8 [‌88‌]
8 M M Me Me 88 8:88 [‌88‌]
8 M Me Me Me 88 8:88 [‌88‌]
8 MMMM (MM8)8MM8Me Me Me 88 8.8:8 [‌88‌]
8 M M Me M 88 88.8:8 (8:8) [‌88‌]
8 eMe M Me M 88 >88:8 (8.8:8) [‌88‌]
8 M M Me Me 88 8.8:8 [‌88‌]
8 eMe M Me Me 88 88:8 [‌88‌]
8 e-Me M Me Me 88 88:8 [‌88‌]

Meeeeeeeeeeeeeee 8,8-eeeeeeee ee e eeeeeeeeeeeeee eeeeeeeeeeee eeeeeee ee ee eeeee eee ee eeeeeeee eeeee eeeeeeee eeeeee eeeeeee ee eeeeeeee eeeeeeee eeeeeeeeeeee eeeeeeee. Meeeeeeeeeeeeee eeeeee 88 eeeee eeeeeeeee eeeeeee ee eee eeeeeeee ee eeeeeee eeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeee (Meeeee 88).[‌88‌] Mee eeeeee ee eee eeeeee eeeeeee ee eeeeeeeee; eeeeeeeeeee eee eeeeee eeeee eeeeeeeeeee eeeeeeee (e.e., Me8Me8Me8) eeee eeee eeeeeeeeeeeeeeeeeeee, eeeeeee eeeeee eeeee eeeeeeeeeee eeeeeeee [e.e., Me8Me(MM)Me8] eee eeeeee eeeee eeeeeeee (e.e., Me8MeMe8) eeeeeee ee eeeeeeeee. Meeeeeeee eeeeeeeeeeeeeeeeeee eee eeeeeeee eee eeeee 8,8-eeeeeeee (eeeeee eee eeeeee), eee eeeeee eeeeeeee eeeee eeeeeee eeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeee ee Meeeeeeeeeee Meeeeeee eeee Meeeeeeeeeeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 (ee Meeeee 88) Meeeeeeeeeee ­Meeeeee (eeeee) M8 Meeee (%) ee (%) Mee
Me MeMe (8) Me 88 88 [‌88‌]
Me Me8Me8Me8 (8.8) Me 88 88 [‌88‌]
eMe Me8Me8Me8 (8.8) Me 88 88 [‌88‌]
eMe Me8Me8Me8 (8.8) Me 88 >88 [‌88‌]
eMe Me8Me8Me8 (8.8) Me 88 88 [‌88‌]
eMe Me8Me8Me8 (8.8) Me 88 e [‌88‌]

e Meeeeee.

Meeeeeeeee 88, eeeeeee eeee eeeeeee, eee ee eeee ee eeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeeee 8,8-eeeeeeee ee eeeeeee ee eeeeeeeee eeeeeeee ee eeeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeee, e eeeeeeee ee eeeeeeeeeeeeeeeeee ee eeeeeeee eeeeeee eeeeeee- eee eeeeeeeee-eeeeeee eeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeee eeeee eee Meeeeeeee ee Meeeeee-Meeeeee Meeeeee[‌88‌]

Meeeeeeee eee ee eeeeeeee ee eee eeeeeeeeeeee eeeeeee ee eee eee ee e eeeeee eeeeeeeeeeeeeee eeeee. Meeeee eeeeeeeeeeeee eeeeeee eeee (M)-M-eeeeee-8-eeeeee-8-eeeeeeeeeeeee­eeeeeee [(M)-MMMM] eeeee eeeeeeeeeeeeeeee 8,8-eeeeeeee ee eeeeee eeeeee 88 eeeeee eeeeeee 88 (Meeeee 88).[‌88‌] Mee eee ee eeeeeee eeeeeee (e.e., MMMMMM) eeeee ee eeeeeee eeeeeeeeeeeeeeeeee ee eeee eeeeeeee.[‌88‌]

Meeeee 88 (M)-M-Meeeee-8-eeeeee-8-eeeeeeeeeeeeeeeeeeee-Meeeeeee Meeeeeeeeeeeeeee 8,8-Meeeeeee[‌88‌]

Meeeeeeeeee 88

e M8 Meeee (%) ee (%) Mee
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]

Meeee(eeee)eeeeee 88, eeeeeee eeee eeeeeee, eeee eeeeeeeeeeee eeeeeeee ee ee 88% eeee eeeeee eeeeee eee eeeeee eeeeee (Meeeee 88).[‌88‌,‌88‌]

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeee eeeee eee Meeeeeeee ee Meeee(eeee)eeeee Meeeeee Meeeeee[‌88‌]

Mee eeeeeeeee-eeeeeee eeeeeeee eeeeee ee eeeeeee 88 ee eeee ee e eeeeeee eee (Meeeee 88). Meeeeee, eee eeeeeeee ee eeeeeee eeeeeeeee ee eeeeeeeeeee ee eeeeeeeeeeeeeeeeee; eee eee ee eeeeeeeee eeeeeeee eeeeeeeeeeee ee, eeee eeeeeeeeeeee, eeeeeeeeeee ee ee eeeeeeee eeeeeeeee ee eeeeeeeee ee eeeeee eeee eeeeeeeeeeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeee eeeee eee Meeeeeeee ee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

e M8 Meeee (%) ee (%) Mee
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 e-Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 Me 88 88 [‌88‌]
8 e-Me 88 88 [‌88‌]

Meeeeee eeeeeee eeeeeee eeee eeee,eeee- eee eee,eee-8-eeeee-8-eeeeeeeeeeeeee eeee eeee eeeeeeee ee eee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeeee eeee eeeeeeeeeeeeeeeeee.[‌88‌] Mee eeeeeee, eeee-eeeeeee 88 eeeeee eeeeeeeee eeee (M)-eeeeeee ee ee eeeeeeee ee eeee eeeee (Meeeee 88).

Meeeee 88 Meeeeeeee ee Meeeeeeee Meee (M)-Meeeeee[‌88‌]

Meeeeeee eee eeeeeeeeeeee eeeeee eeeeeee ee eeeeeee eeeeeeeeeeeee eeeeeee eeeeeee eeeeeeeeeeeeeeeee ee eee α-eeeeeeee ee eee eeeeeeeee eeeeee.[‌88‌] Meeeee eeeeee eeeeeee eeeeeeeeee eeeeeeee eeeeee eeeeee eeeeeeee eeee ee eeeeee, eeeee, eeeeee, eeeeeeeee, ee α-eeeeeeee eeeee eeeeeee. Meeeeeeeeee ee eeee eeeeee eeeeeeeee ee eeeeeeee ee eeeee eeeeeeeeeeeeeeeeeeee eeeeeeee ee e eeeeeeeee, ee eeeeeeee eee eeeeeee eeeeeeeeee eeee eeeeeee ee eeeeeeeee.[‌88‌] Me eeeeeee eeeeeeeee ee eeeeeeeeeeeee M8 eeeeee ee eeeeee eeeeeeeee eeeeeeee/eeeeeee eeeeeeeeee. Me eeee eeeeeeeeeeeeeeee ee eee eeeeeeeeeeee eeeeee eeeeeee ee eeeeeeeeeeeeeeeeeeeeeee ee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee Meeeeeeee Meeeeeeeeeeee M8 Meeeee Meeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee 88 ee Meeee Meee Meeeeeee Meeeeeeeeee Meeeeeee; Meeeeee Meeeeeeee:[‌88‌]

Me e 888-eM eeeee, eeeeeeee eeee e eeeeeeee eeeeeee eee eeeeeeeeee eeeee M8, eeee eeeeee MeM (8.8e, 88eeee) eee eee Me8M (88eM). 8.8M MeMe ee eeeeee (88eeee) eee eeeee ee 88°M eee eee eeeeeeeee eeeeeee eee eeeeeee ee eeee eeeeeeeeeee eee 88eee. Mee eeeeeee eee eeee eeeeee ee eeeeeee 88 eee 88°M eee e Meeee eeee [MM8MMe8 (88%; 8.8eM, 88eeee), MeMe8MMe8 (88eeee), ee Me8MeMeMMe8 (88eeee)] eee eeeee. Meeee eee eeeeeee eee eeeeeee eee e eeeee, eeeee 88 (88eeee) eee eeeee, eee eeeeeee eee eeeeeee ee eeeeee eeee ee ee eeee eeeeeeee, eee eee eeee eeeeee ee 8°M. Mee eeeeeeee eee eeeeeeee eeee eee. ee MM8Me eeee, eeeeeeeee eeee Me8M (8×), eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8).

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

(M)-M-Meeeee-8-eeeeee-8-eeeeeeeeeeeeeeeeeeee (888ee, 8.8eeee) eee eeeeeeeee ee eee Me8M (88 ee), eee 8.8M MeMe ee eeeeeee (8.88eM, 8.88eeee) eee eeeee ee eee eeee ee 88°M. Mee eeee eee eeeeeee eee 8eee ee 88°M eee eeeeee eeeeeeeee ee 8°M. Me e eeeeeeee eeeee, MeMe (8.88eM, 8.88eeee) eee eeeee ee e eeeeeeeeee ee MeM (888ee, 8.88eeee) ee Me8M (88eM) ee 88°M, eeeeeee e eeeeeeeeee ee MeMe. Mee eeeeeee eeeee eeee (eeeee eeee) eee eeeeee ee 88°M eee eeeee eee eeeeee ee eee eeeeeeeeee ee MeMe, eeee ee 88°M. Meeee eeeeeee eee, eee eeeeeeeee eeee eee eeeeee ee 88°M. Meeee 88eee, 8-eeeeeeeeeeeeee (88, e=8; 888ee, 8.88eeee) eee eeeee eeeeeeee eee eeeeeee. Mee eeeeeee eee eeeeeeee eeeee 8e ee eeeeee 8M MM8Me (88eM) eee eeee eeeeeeeee eeee Me8M (88eM). Mee eeeeeee eee eeeeee eeee 8M MMe (88eM), eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 88:8) ee eeeeee eee eeeeeee; eeeee: 888ee (88%); 88% ee.