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3.1.11.1.1.3 Variation 3: Zinc-Catalyzed Mannich Reaction

DOI: 10.1055/sos-SD-103-00147

Wu, X.-F.Science of Synthesis Knowledge Updates, (20141274.

In 2000, Ishimaru and co-workers reported zinc-mediated Mannich-type reactions.[‌74‌‌76‌] In the presence of 2 equivalents of zinc(II) trifluoromethanesulfonate and 2–3 equivalents of water, 2-siloxybuta-1,3-dienes react with imines under mild conditions. Moderate to excellent yields of the corresponding products are formed, and the presence of water is crucial for the success of this reaction. Later on, it was proved that this reaction can even be promoted by trifluoromethanesulfonic acid alone.[‌77‌] A catalytic version was developed by Shi and co-workers more recently.[‌78‌] The reaction of hydrazones 23 with difluoroen­oxysilanes 24 to afford chiral oxo hydrazines 25 occurs in the presence of 10 mol% of ­zinc(II) trifluoromethanesulfonate; the asymmetric reaction was performed similarly using zinc(II) bis(trifluoromethylsulfonyl)amide in the presence of dihydroimidazole-an­chored phosphine ligand 22 (Scheme 9).[‌79‌]

Meeeee 8 Meee-Meeeeeeee Meeeeeeeee Meeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 8

Me8 Me8 Meeee (%) ee (%) Mee
8-MeM8M8 Me 88 88 [‌88‌]
8-Mee Me 88 88 [‌88‌]
8-M8MM8M8 Me 88 88 [‌88‌]
8-eeeeeeee Me 88 88 [‌88‌]
8-eeeeeee Me 88 88 [‌88‌]
8-MeM8M8 Me 88 88 [‌88‌]
8-MeM8M8 8-Mee 88 88 [‌88‌]
8-MeM8M8 8-eeeeeee 88 88 [‌88‌]

Mee Meeeeee eeeeeeee ee eeeeee eeee eeeee eeee eeeeee eee eeeeeeee eeee e eeeeeeeee eeeeee ee eeee(MM) eeeeeeeeeeeeeeeee ee eeeeeee eeeeeeee.[‌88‌] β-Meeee eeeeeeee eeeeeeeee 88 eee 88 eee eeeeeeee ee eeee eeeeee ee eeee eeeeeeeeeee eeee eeeeee eee eeeee eeee eeeeee, ee eee ee eeee eeeeeeeee ee eee eeeee eeee eeeeeeeee eee eeeeee (Meeeee 88). Meee–M,M′-eee(eeeeeeeeeeee)eeeeeeeeeeeeeeeeee eeeeeee 88 ee eeee eeeeeeeee eee eeee eeeee-eeeeeeeee eeeeeeee ee eeeeeee β-eeeee eeeeeeeeee eeeeeeeee 88.[‌88‌]

Meeeee 88 Meee-Meeeeeeee Meeeeee Meeeeeee ee Meeeeeeee[‌88‌,‌88‌]

Mee Meeeeeeee eeeee eee eeeeeeeee e eeeeee eeeeeeeeeeeeeeee Meeeeee eeeeeeee ee eeeeeee eeeeeee eeee M-(eeeeeeeeeeeeeeeeee)eeeeee 88 eeeee eeeee 8,8′-ee-8-eeeeeeee-eeeee eeeeee 8.[‌88‌‌88‌] Me eee eeeeeeeeeee ee eeeeeeeeeee eee eeeeee 8 ee −88 °M ee eeeeeeeeeeeeeee, eee eeeeeeee eeeeeeee 88 eee eeeeeeee ee eeeeeeeee eeeeee eeee eeeeeeeee eeeeeeeeeeee eeeeee (Meeeee 88). Mee eeeeeeeee eeee eeeeeeee 8 eeee Meeee ee eeee eeeeeeeee eee eeee eeeeeeeeeeeeee, eeeeee eeeeeeee eee-88 eeee eeeeeeee eeeeeeee eeeeeeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meee-Meeeeeeee Meeeeeeeee Meeeeee Meeeeeee ee Meeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 Me8 Meeeeeee Meeee (%) ee (eeee/eee) eee (%) Mee
8-Mee 8-MeMM8M8 8, Me8Me 88 88:8 88 [‌88‌]
8-Mee 8-MeMM8M8 8, Me8Me 88 >88:8 88 [‌88‌]
8-MeMM8M8 8-MeMM8M8 8, Me8Me 88 88:8 88 [‌88‌]
8-M8MM8M8 8-MeMM8M8 8, Me8Me 88 88:8 88 [‌88‌]
8-MeM8M8 8-MeMM8M8 8, Me8Me 88 88:8 88 [‌88‌]
8-eeeeeeee 8-MeMM8M8 8, Me8Me 88 88:8 >88.8 [‌88‌]
8-eeeee 8-MeMM8M8 8, Me8Me 88 88:8 >88.8 [‌88‌]
Me Me 8 88 8:8 88e [‌88‌]
eMe Me 8 88 8:8 >88e [‌88‌]
(MM8)8Me Me 8 88 8:8 88e [‌88‌]
(MM8)8Me Me 8 88 8:8 88e [‌88‌]
Me 8-MeMM8M8 8 88 8:8 88e [‌88‌]
eMe 8-eeeeeeee 8 88 8:8 88e [‌88‌]
eMe 8-eeeeeeee 8 88 8:8 88e [‌88‌]

e Me eee eeee-eeeeeeeeeeee.

e Mee eeeee eeeeeeeeee eee eee-88.

Meeeeeeeeeee Meeeeeeee

M′-[(M)-8-(8-Meeeeeeeeeee)-8,8-eeeeeeee-8-eee-8-eeeeeeeeeeee]eeeeeeeeeeeeee (88, Me8 = 8-MeM8M8; Me8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Me(MMe8)8 (8.88 eeee) eee eeeeee eeeeeeeeeeeeeeee eeeeeeeee eeeeee 88 (8.88 eeee) eeee eeeee eeee e Meeeeee eeee eee eeee MeMM/MMM (8:8; 8.8 eM) eee eeeee eeee eee eeeeeeee eeeeee. Mee eeeeeeeee eeee eee eeeeeee eee 8.8 e ee ee (88 °M). Meee, eeeeeeeee 88 (Me8 = 8-MeM8M8; 8.88 eeee) eee eeeee, eee eee eeeeeee eee eeeeee ee 8 °M. Meeeeee eeeeeeee eeeeeeeeeeeeeeeeeee 88 (Me8 = Me; 8.88 eeee) eee eeeee eeeeeeee ee eeeeeee. Mee eeeeeee eee eeeeeee eee 88 e ee 8 °M. Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee eee. ee MM8Me (8.8 eM) eee eee eeeeeee eee eeeeeeeee eeee MM8Me8. Mee eeeeeee eeeee eee eeeeee eeee eeeee eee eeeee (Me8MM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee) ee eeee eee eeeeeeeeeeeee eeeeeee ee e eeee eeeeee eee; eeeee: 88 ee (88%); 88% ee ee eeeeeeeeee ee MMMM [Meeeeeeee MM-M, eeeeee/eMeMM 88:88, 8.8 eM·eee−8, 888 ee; eM = 88.88 (eeeee) eee 88.88 eee (eeeee)]; [α]M88 +88.8 (e 8.88, MMMe8); MM (eeeeeee) ν̃eee: 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888, 888, 888 ee−8; 8M MMM (888 MMe, MMMe8, MMM, δ): 8.88 (e, 8M, M = 88.8 Me, MM), 8.88 (ee, 8M, MM), 8.88–8.88 (e, 8M, MeM), 8.88–8.88 (e, 8M, MeM), 8.88 (e, 8M, M = 8.8 Me, MeMM), 8.88 (e, 8M, M = 8.8 Me, MeM); 88M MMM (88 MMe, MMMe8, MMM, δ): 88.8 (ee, MM-M = 88.8, 88.8 Me), 888.8 (e, MM-M = 888.8 Me), 888.8, 888.8, 888.8, 888.8, 888.8 (e, MM-M = 8.8 Me), 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8 (e, MM-M = 88.8 Me); 88M MMM (888 MMe, MMMe8, MMM, δ): −888.8 (ee, 8M, M = 888, 88 Me), −888.8 (ee, 8M, M = 888, 88 Me).

8,8-Meeeeeee-8-(eeeeeeeeeee)eeeeee-8-eee (88, M8 = M8 = Me; M8 = M8 = M); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee M-eeeeeeeeeeeeeeeeee (888 ee, 8 eeee) eee 8-eeeeee-8-(eeeeeeeeeeeeeee)­eeeeee (888 ee, 8 eeee) ee M8M/MMM (8:8; 8 eM) eee eeeeeee eeee 88% ee Me(MM8)8 (8.88 eM, 88 eee%; Meeeeee) ee ee (88–88 °M) eee 8 eee. M eeeee eeeeeeeee eee ee eee eeeeeeee eeeeee. Mee eeeeeee eee eeee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee Me8M eeeeeee eee eeeeee eeee eeeee eee eeeee (Me8MM8). Meeeeeeeeee ee eeeeeee eeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 8:8) ee eeee eee eeee eeeeeee; eeeee: 888 ee (88%).

8-[Meeeee(eeeeeeeeeee)eeeeee]eeeeeeeeeeeee [88, M8 = Me; M8 = M; M8,M8 = (MM8)8]; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeeeeee ee eeeeeee (888 ee, 8.8 eeee) eee MeMMM (888 ee, 8 eeee) ee M8M/MMM (8:8; 8 eM) eeee eeeee 8-(eeeeeeeeeeeeeee)eeeeeeeeeee (888 ee, 8 eeee) eee 88% ee Me(MM8)8 (8.88 eM, 88 eee%; Meeeeee) eee eee eeeeeee eee eeeeeee ee ee (88–88 °M) eee 88 eee. M eeeee eeeeeeeee eee ee eee eeeeeeee eeeeee. Mee eeeeeee eee eeee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee Me8M eeeeeee eee eeeeee eeee eeeee eee eeeee (Me8MM8). Meeeeeeeeee ee eeeeeee eeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 8:8) ee eeee eee eeee eeeeeee; eeeee: 88%.

β-Meeee Meeeeeeeeee 88; Meeeeee Meeeeeeee eee Meee-Meeeeeeee Meeeeee Meeeeeee ee Meeeee Meeeeeeee Meeeeeeee:[‌88‌]

Me e eeee ee Me–eeeee eeeeeeee 88 (8.88 eeee) ee MM8Me8, eee eeeeeeee (8 eeee), eee eeeee (8 eeee), eee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeee eeeeeeee (8 eeee) eeee eeeee, ee eeeeeeee. Mee eeeeeee eee eeeeee ee eeeeee eee 8 e. Mee eeeeeee eee eeee eeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeeee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe).

(8M,8M)-8-[(Meeeeeeeeeeeeeeeee)eeeee]-8-eeeeeee-8-(8-eeeeeeeeeeeee)-8-(8-eeeee)eeeeee-8-eee (88, M8 = 8-Mee; Me8 = 8-MeMM8M8); Meeeeee Meeeeeeee eee Meee-Meeeeeeee Meeeeee Meeeeeee eeee Meeeee 8:[‌88‌]

Me e eeee eeee, 8-Å eeeeeeeee eeeeee (888 ee) eeee eeeeeeeee eeeee ee eee eeeee eeeeeee eeeeeeee (ee. 8.8 eMe) ee 888 °M eee 8 e. Meeee eee eeee eee eeeeee ee ee, ee eee eeeeeeee eeee eeeee eee e eeee ee eeeeee (M,M)-8,8′-ee-8-eeeeeeee eeeeee 8 (8.88 ee, 8.88 ee% Me8M eee eeeeee eeeeeeee, 8.888 eeee) ee MMM (888 µM) eee eeeeeee. Me eeee eeeeeeeeee eee eeeee e 8.8 M eeee ee Me8Me ee eeeeeee (88 µM, 8.88 eeee). Meeee eee eeeeeee eee eeee eeeeeee eee 88 eee ee −88 °M, e eeee ee 8-eeeeeee-8-(8-eeeeeeeeeeeee)eeeeeeee (888.88 ee, 8.8 eeee) ee MMM (8.88 eM) eee M-(eeeeeeeeeeeeeeeeee)eeeee 88 (M8 = 8-Mee; 888.88 ee, 8.8 eeee) ee MMM (8.8 eM) eeee eeeee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeee ee eee eeee eeeeeeeeeee eee 8 e. Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee eee. ee MM8Me eee eee eeeeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee eee eeeee (Me8MM8). Meeeeeeeeee ee eeeeeee eeee e eeeee eeeeeee ee eee Meeeeee eeeeeeee. Mee ee (88:8) eee eeeeeeeeee ee 8M MMM eeeeeeee ee eee eeeee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe) ee eeee eee eeee eeeeeee ee e eeeeeeeee eeee; eeeee: 88%; 88% ee ee eeeeeeeeee ee MMMM [MMMMMM Meeeeeeee MM, eMeMM/eeeeee 8:8, 8.8 eM·eee−8, 888 ee; eM = 8.8 (eeeee) eee 88.8 eee (eeeee)]; [α]M88 +88.8 (e 8.8, MMMe8); MM (MMe) ν̃eee: 8888, 8888, 8888, 8888 ee−8; 8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (ee, M = 8.8, 88.8 Me, 8M), 8.88 (eee, M = 8.8, 88.8, 88.8 Me, 8M), 8.88 (ee e, M = 8.8, 8.8 Me, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88 (ee, M = 8.8, 88.8 Me, 8M), 8.88 (ee, M = 8.8, 88.8 Me, 8M); 88M MMM (MMMe8, δ): 88.8, 88.8, 88.8, 88.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8.

(8M,8M)-8-Meeeeeeeee-8-[(eeeeeeeeeeeeeeeeee)eeeee]-8-eeeeeee-8-eeeeeeeeeeee-8-eee (eee-88, Me8 = Me; M8 = Me); Meeeeee Meeeeeeee eee Meee-Meeeeeeee Meeeeee Meeeeeee Meeee Meeeeeeee Meee Meeeeeee 8:[‌88‌]

Meeeeee 8-Å eeeeeeeee eeeeee (88 ee) eeee eeeee-eeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeee eeee ee ee, eee eeeeee (8 ee, 8.8888 eeee) eee eeeee eee M8 eee eeeeeeee. MMM (8.8 eM) eee eeee eeeee. Me eeee eeeeeeeeee eee eeeee eeeeeeee e 8.8 M eeee ee Me8Me ee eeeeeee (88 μM, 8.888 eeee) ee ee eee eee eeeeeee eee eeeeeee eee 88 eee. Meeee eee eeeeeee eee eeee eeeeee ee −88 °M, e eeee ee 8-eeeeeee-8-eeeeeeeeeeeeee (88 ee, 8.88 eeee) ee MMM (8.88 eM) eee M-(eeeeeeeeeeeeeeeeee)eeeee 88 (M8 = Me; 88 ee, 8.8 eeee) ee MMM (8.88 eM) eeee eeeee eeeeeeeeeeee. Meeee eee eeeeeee eee eeee eeeeeee ee −88 °M eee 88 e, ee eee eeeeeee eeee Me8M (8 eM) eee eeee e eM 8 eeeeeeeee eeeeee (8 eM) eee eeeee. Mee eeeeeee eee eeeeeee eee 88 eee. Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 8 eM). Mee eeeeeeee eeeeeeee eeee eeeeee eeee eeeee (8.8 eM), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee ee eeee e eeeee eeeeeee ee eee Meeeeee eeeeeee. Mee ee (8:8) eee eeeeeeeeee ee 8M MMM eeeeeeee ee eee eeeee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 8:8 eeee MeMMe) ee eeeee eee eeeeeee eeeeeee ee e eeeee eeeee; eeeee: 88%; ee 88–88 °M; Me 8.88 (MeMMe); 88% ee ee eeeeeeeeee ee MMMM [Meeeeeeee MM, eeeeeee/eMeMM 88:88, 8.8 eM·eee−8, 888 ee; eM = 88.8 (eeeee) eee 88.8 eee (eeeee)]; [α]M88 −8.8 (e 8.88, MMMe8); MM (eeee) ν̃eee: 8888, 8888, 8888, 8888, 8888, 8888, 8888, 8888 ee−8; 8M MMM (888 MMe, MMMe8, δ): 8.88–8.88 (e, 8M), 8.88 (ee, M = 8.8, 8.8 Me, 8M), 8.88–8.88 (e, 8M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (ee e, 8M), 8.88 (ee e, M = 8.8 Me, 8M), 8.88 (ee, M = 88.8, 8.8 Me, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M); 88M MMM (888 MMe, MMMe8, δ): 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.88, 888.88, 888.88, 888.8, 888.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8.

References


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