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7.1.9.11.1.2 Conjugate Addition

DOI: 10.1055/sos-SD-107-00059

Oishi, M.; Takikawa, H.Science of Synthesis Knowledge Updates, (2010497.

Asymmetric conjugate additions have attracted increasing synthetic interest.[‌21‌,‌22‌] Excellent enantioselectivities can be achieved using mainly organozinc reagents in the presence of copper catalysts. However, since a number of organoaluminums are either commercially available or readily prepared, they provide significant potential for application in this area. Since the mid-2000s, many effective chiral ligands have been developed for the copper-catalyzed asymmetric conjugate addition of triorganoaluminums with various Michael acceptors, as discussed below.[‌23‌,‌24‌]

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M8 M8 Meeeee (eee%) Meeeeeeeee ee (%) Meeee (%) Mee
(MM8)8Me Me 8 (88) [Me(MMMe)8]MM8 (88 eee%), MMM, −88 °M 88 88 [‌88‌]
eMe Me 8 (88) [Me(MMMe)8]MM8 (88 eee%), MMM, −88 °M 88 88 [‌88‌]
Me Me 8 (88) [Me(MMMe)8]MM8 (88 eee%), MMM, −88 °M 88 88 [‌88‌]
(MM8)8Me Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]
(MM8)8Me Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]
eMe Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]
eMe Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]
Me Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]
Me Me 88 (8) MeMM (8–8 eee%), Me8M, −88 °M 88 88 [‌88‌]

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

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Meeeee 8 Meeeee-Meeeeeeee Meeeeeeeee Meeeeeeee Meeeeeeee ee Meeeeeeeee ee Meeeee Meeeee[‌88‌]

Meeeeeeeeee 8

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

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Meeeeeeeeee 8

e M8 M8 M8 Me Meee Meeeee ee (%) Meeeeeeeee (%) Meeee (%) Mee
8 Me Me Me MeMM 88 88 >88 e [‌88‌]
8 Me Me Me MeMM 88 88 >88e 88 [‌88‌]
8 Me Me Me MeMM 88 88 e 88 [‌88‌]
8 eMe Me Me (MeMMe)8•eeeeeee 88 88 >88e 88 [‌88‌]
8 Me Me MMe═MM8 MeMM 88 88 888e,e 88 [‌88‌]
8 Me Me Me MeMM 88 88 88e 88 [‌88‌]
8 Me Me Me Me(MMe)8 88 88 >88e 88 [‌88‌]
8 Me Me 8-Mee Me(MMe)8 88 88 >88e 88 [‌88‌]

e Mee eeeeeeee.

e Meeeeeee eeeeeeee (eee eeee).

e Meeeee/eeeeeee eeeeeeee = 8:88.

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References