You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.1.1.7 Iminium Catalysis
Please login or sign up for a free trial to access the full content.
MacMillan, D. W. C.; Watson, A. J. B., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 309.
General Introduction
a,B-Unsaturated carbonyl compounds are one of the most synthetically valuable classes of substrates available to the preparative chemist. These species have enjoyed such a distinguished position for over 120 years due to the reactivity imparted to the alkenic moiety by the electron-withdrawing carbonyl vector, which enables fundamental synthetic transformations such as the 1,4-addition category of chemical bond formations.[1] Since the discovery of the first conjugate addition process by Komnenos in 1883,[1–3] the 1,4-addition reaction has become a mainstay of chemical synthesis, affording a host of powerful carbon—carbon and carbon—heteroatom bond-forming technologies. The potential to develop asymmetric processes was quickly realized, using a number of different approaches, and continues to be an area of intense research activity.[1,4–13]
Mee eeeeeeeee eeeeeeeeeee ee eeeeeeeeee 8,8-eeeeeeee eeeeeeeee ee eeeee ee eeee eee a,B-eeeeeeeeeee eeeeeeeee eee eee eeeeeeeeeeee eeeeeeeee eee eeeeeeee eee eeeeeeee eeeeeeeee eeee e eeeeeee, eee eeeeeeeeeee eeeeeeeee, eeeeee eee eee eeeee eeeeeeeeeeee ee eeeeee—eeeeee eee eeeeee—eeeeeeeeee eeeeeeeeeeeeee. Meeeeeeeeeee, eeeee eee eeeeeeee eeeeee eee eeeeeeeeee eeeeeeee eeeee eeeeeeeeeeeee, eeeee eee eeeeeeeeeeee ee eeeeeee eeeeeeeeeeeeee eeeee e eeeeeee ee eeeeeeeeeee eeeeeeeee, eeeeeeeeeeeeeeee 8,8-eeeeeeee eeeeeeeee eeeeeee eeeeee ee e eeee ee eeeeeeee eeee eeeeeeeeeeeee eeeeeee eeeeeeeee eeeee eee eeeeeee eeeeeee. Meeeeeeeeee, eee eeeeeeeee eeeeeeeeeee ee eee eeeeeeeee eeeeeeeeeeee eeee eeeeeee eeee eee eeee-eeeeeee eeeeeeee ee ee eeeeee eeeeeeee.
Me eeee eeeeeee, eeee eee eeeeeeeeeee ee eee eeeeeeeeee eeee ee Meeeeeeeeee eeeeeeeee eeee 888 eeeee eee[88,88] eee eeeee eeee eee eeeeeee eeee ee Meeeeeeeee ee eee 8888e,[88] eeeeeeeeee ee ee a,B-eeeeeeeeeee eeeeeeee ee eeeeeeeeeeee eeee e eeeeee eeeee eeeeeeee, ee eeeeeee eee eeeeeeeeeeeee eeeeeee eeeeeee eeeee eee eeee eeeeeeeeeee ee eeeeeeeeeeeeeeee 8,8-eeeeeeee eeeeeeeee, eee eeee eeeee eee eeee 88 eeeee. Meeeeeeee eeeee eeeeeeeee eee eeeeeeeee eee eeeeeeeee eeeee ee eeeeeee eeeeeeeeeee ee eeeeeeeee ee eeee eeee eeeeeee e eeeeee ee eeeeeeeeeeee ee eee 8888e.[88–88] Me eeeeeeee ee eeee, eeeeeee eeeee eeeeeeeee eeeeeee ee eeee eee eeee ee ee eeeeeeeee eeeee ee eeeeeee eeeeeeeeee eeee eeee eeeeeeeeee.[88,88] Meeeeee, ee eee eee eeeee 8888 eee eee eeeeee ee eeeeeeeeeeeeeee eeee eeeeeee eeeeeeeee[88–88] eee eeeeeeeeee ee e eeeeeee eeeeeeeeee eeee eee eeeeeeeeee eeeeeeeee eeeeeee MeeMeeeeeʼe eeeeee, eeeee-eeeeeeeee eeeeeeeeeeeeeeee Meeee–Meeee eeeeeeee.[88]
Meee eeeeeeeeeeeeeee eeeeeeee eee eeeeeee ee eee eeeeeeeeeee eeeeeeeeee eeee eee eeeeeeeeee eeeeeeeee ee eeeeeee eeee, eeee a,B-eeeeeeeeeee eeeeeeee eeeeeeeee eee eeeeee eeeeeeeee eeeeee, eeeee eeeeeee eee eeeeeeeeeee eeeeeeee eee π-eeeeeee eeeeeeeeeee eeee eee eeeeeeee ee Meeee eeee eeeeeeeee, e.e. MMMM-eeeeeeee eeeeeeeeee (Meeeee 8).[88]
Meeeee 8 Meeee Meee Meeeeeeee eee Meeeeee Meeeeeeee: Meeeeeeeeeeeeeee 8,8-Meeeeeee eee MMMM-Meeeeeee Meeeeeeeee
Meee eee eeeeeee eeeeeeeeeee eeeeeeee eee eeeeeeeeeee eee e eee eeee ee eeeeeeee eeeeee eee eeeeeeeeeeeeeeee 8,8-eeeeeeee eeeee eee eee eeeee eeee eeeeeeeee eeeeeeeeeeee.[88–88] Meeeeeeeeeee eeeeeee eeee eeee eeee eeeeeeee eeeeee eee eeeeeeeeeeeeee ee eee eeeeeeeeee ee eeeeeeeeeeeeee ee eeeeeee eee eeeeeeeee eeeee eee eeeeeeee eeeeeee eeeeeeee ee eee eeeeeee eeeeeeeee eeeeeeee, eeeeeeeee e eeeeeeee ee eeeeee eeeeeeeeeeeeeeee eeee-eeeeeee eeeeeeee eeeee. Meeeeeeeeeee, eeeeeee eeeeeeeee eeeeeeeeeeee (eee, eeeeee, eeeeeeeeeeeeeee ee eeeeeee) eee eeeeeeeee eeeeeeeeeee eeeeeeeeee eeeeeeeeeee eeeeee eeeeeee eeeeeeee eeeeeeeee.[88]
Meee eeeeeee eeeeeeeee eee eeeeeeeeeee ee eeeeeee eeeeeeeee eeeeee eee eeeeeeeeeeeeeeee eeeeeeeeeeee ee eeeeee—eeeeee eee eeeeee—eeeeeeeeee eeeee. Meeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeeee (Meeeeee 8.8.8.8) eee B-eeeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeee (Meeeeee 8.8.8.8). Meeee eeeee ee ee eeeeeeeee eeeee ee eeeeeee eeeeeeeee eeee eeeeee eeeeeee eeeeeeeee ee e eeeeeee eeeeeee, eeee eeeeeee eeee eeeeeeeee eeeee ee eeeeee eee eeeee ee eeee eeeeeee. Meeeeee, eeeeeee-eeeeeeeee eeeeee [8 + 8]-eeeeeee eeeeeeeeeeeee eeeeeeeee (eeeeeeeeeeeeeeee, eeeeeeeeeeeee, eee eeeeeeeeeee) eeee eeee eeeeeeee (Meeeeee 8.8.8.8).
Meeee eee eeeeeee eeeeeee eeeeeee ee eeeeeee eeeeeeeee eeee eeeeee ee eeeee eee eeee eeeeee ee eeeee ee eeeeeee eeeee eeeee ee eeeeeeeee eeee eeeeeeeeee eeee, eeeeeeeeeeee ee eeeeeeeeee eeee eee eeeeeeee (ee ee eeeee eeee eeee eee eeee eeeeeeeeeeee ee eee eeeeeeee eeeeeeeeee). Meeee eeeeeee eeeeee eee eeeeeeee eeeee eee eee eeeeeeeeeeee eeee eeee eeeeeeee eeeeeeee eeeeee eee eeeeeeee eeeeeee eeeeeee.
Meeeeeee Meeeeeeee: Meeeeeeee ee e eeeeeeee eeeeeeee ee eeeeeee ee eee eeeeeeeeee eeeeeee ee eee eeeeeeeeeeeee ee 8,8-eeeeeeee eeeeeeee. Meeee eeee eeeeee eee eeee ee eeeeeeee eee eeeeeee-eeeee eeee-eeeeeee eeeee, eee eeeeeeee eeeeeeeeee/eeeeee eee eeeeeeeeeeeeee eeeeeeeee eeeeeeeeeeee ee eeeeeeeee eee eeee eeeeee. Me eeee ee eeee, eeeee eee eeeeeee eeeeeeeeee eeeeeeee eeeeeeeeee, eeee ee eeeee eee eee eeeeeeeeeeee eeeeeeeee ee eee ee eeee ee eeeeeee eeeeeeeeeeeeeee eeeee. Meeeeee, ee eeeeee ee eeeee eeee eeee ee eee eeee eeeeeeee-eeeeeeee eeeeeeeee eee eeeeeee e eeee eeeeeeeee eeeeeeeeeee. Me eeeeeeee, eeee eeeeeeeeeee eee eeeeeeeee eee eeee eeeeeeeee eee eeee eeeeeeeee eeeeeeeee eee eeee eeeeeeeeee eeeeee eee eeeeeeee eeeeeee. Meeeee, ee ee eee eeeeeee eee eeeeeeeee ee eeeee eeee eeeeeeeeeee eee eeeeeeeee ee eee eee eeee eeeee eeeeeeee eee ee e eeeeeeeee eeee eeee. Meeeeeeeee ee eee eeeeeee eeeeeeeee eeee eeee eeee eeeee ee eeeeeeeeeee eeeeeee e eeeeeeeeee eeeeeeeeeeeeee eee eeeeeeee eee eeee eeeeeeee eeee.
Meeeeeee Meeeeee: Meeeeeeeeeeeee eeeeeeee eee eeee eeeeeeeeeeeee eeeeeeeee ee eee eeeeeee eeeeeeeeeeeeee. Meeeeeee eee ee eeeeeeee eee [e.e., 8 eee% (8.88 eeeee) eee eeee eeee eeee eeeeeeeee eeee eee eeeee eeeeee] ee eeeeeeeeeeee eeeeee [e.e., 88 eee% (8.8 eeeee)]. Me eeeeeee, e eeeeeee ee 88 eee% (8.8 eeeee) eeeee ee e eeeeeeee eeeeeeee eeeee eeee eeeeeeeeee e eeeeeeeeeeeeee ee ee eeeeeee eeeeeeeee.
Meeee: Meee eeeeeee-eeeeeeeee eeeeeeeee eee eeeeeeeee ee e eeeeeeeeee eeeee ee eeeee, eeeeeeee eeee eeee eeee eeeeeeeee ee e eeeeeeeeeeee eeeeee (eeeeeeeee) eeeee.
Meeeeee Meeeeee: Meee eee eeee eeeeeeeeeeeee eeeeeeeee ee eee eeeeeeeeeeeeee eee eeee eeeeee ee eeeee ee eeee eee eeeeeeee eeeeeeeeee ee e eeeeeeeeee eeeeeeeee. Meeeeeeee eeeee eeeeee eee eeeeeeeeee eeeeeeeee ee eee eeeeeeeeeee ee eee a,B-eeeeeeeeeee eeeeeeee eeeeeeeee eeeeeeee eeeee eeee eeeeeeeee eee eee eeeeeeee eeeeeeeee ee eeeeee. Meee eee ee eeeeeeeeee eeeeeeeeeee eeee eeeeeeeeeee eee ee ee eeeeeeee eeeeeeeeeeee eeee ee eeeee eeee eee eeeeeeee eeeeeeee eeeee ee eeeeeee. Meeeeeee eeeeeeeeee eee eeee eeeeee eeeeeeeee ee eee eeeeeeee eeeeeeeeee eeeeeeee eee eee eeeeee eeeeee ee eee eeeeeee eeeeeeeeee eee eeee eeeeeee eee eeeee ee eee eeeeeeee eeeeeee.
Meeeeeee Meeeeeeeeee: Meeeeeeee eeeeeeee eeeeeeee, eeee eeeeeeeee eee ee eeeeeee eee eeeeeeeeeeee ee eeee eeeeeeeeeee eeeee eeee eee eeeeee eee e eee eee eeeeee. Meeeeeeeeeee eee eee eeeeeeee eeeeeeee eee eeee eeeeeee eeeee eeee −88 ee +88 °M.
Meeeeeee Meee: Meee eeeeeee-eeeeeeeee eeeeeeeee eee eeeeeeee eeee eee eee eeeeeeee eeeeee e eee eeeee ee eeee, eeeee eeeeee eee eeeeeee eeeeeeeeeeeee eeeeee eeee eeeeeee. Meeeeeeee eee eeeeeeeee eeeeeeeee ee MMM, 8M MMM, MM, MMMM, ee MMM eee eeeeeeeeeee ee eee eeeeeeee eeeeeee.
Meeeeee Meeeeeeee: Meeee eeeeeeee, eee eeeeee eeeeeeee ee e eeeeeeeeee eeeeeeeeeeeeee eeee eeee eeeeeeee, eeeeeeee eeeeeeeeeeeeee eeeee eee eee eeeeeeee, eeeeeeeeeeee eeee eeeeeeeee ee eeeee eeeeeeeee ee eee eeeeeee (eeeeeeeee eeee MeMM8) ee eee eeeeeeeeeeeeee eeee eeeee eeeeeeee. Meeeeeeeeeee, eeeee eee eeeeeeee ee eeeee eeee eee “eeeeeeeeee eeeee” ee eeeee, e.e. eee eeeee ee eeeeeeee eeee e eeeeeeeeee eeeeeeeeee eeeeeeeeee, eeeeeeeee eeeeeeeee eeeee ee eeeeeeee eeeeeeee.
Meeeeeee: Meeeeeee ee eeeeeeeeee eee eeeeeeeeeeeeeeeeee eee eeeeeeee eeeee e eeeeeeeeeee ee MMM, MM, MMMM, eee/ee MMM eeeeeeeeee. Mee eeeeeeeeeee, eee eeeee eeeeeeee, eee eeeeee ee eeeeeeee ee eeeeeeeeeee eee e eeeeeeee eeeeeee eee eeee eeeee. Meeeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeee eeeeeeee eeeeeeeeeeeeee, e.e. ee eee eeeeeeeeeeeee eeeeeee.
Meeeeee: M eeeeee eeeeeeeeeeeee ee eeeeeee ee eee e eeeeeeeeeeeeee eeee ee eeeeeeeeee ee ee eeeeeeee (ee eeeeeeeeeee) eeeeeeeee ee eeeeeeeee. Meeeeee ee eee eeeeee eeeeeeee eeeeeeeee eeeeeee eeeeeeee eeeeeeeeeee eeeeeeeeee eeeeee eeee ee eeeeee, eeeeeeeeee, eeeeeee, eee eeeeeeee/eeeeeeeeeeeeee eeeeeeee eeeeee eeeee eeeeeee eeee; eeeeeee, eeee eeeeeeeeeee eeeeee eeee eeee eeeeee eeeeeeeeee. Meeeeeeeee ee eeeeeeeeeeee eeeeeeeee eeeeee eeeeeeee eeeeeeee ee eeee eeeeeeeeeeee eeeeee ee eeeeeee eee eeeeeeeeee ee eeeeeee ee eee eeeeeeeeee eeeeeeee, ee eeee ee eeee, eeee eeeeeeeeeee ee eee eeeeeeeeeee ee eee eeeeeeeee eeeeeeeeeeee (eee eeeeeeeeeee eeeeee eeee eeee) eee ee eeeeeeeeeeeeeee eee ee eeeeeeeee.
Meeee Meeeee: Meeee eeeeeeeeee eeee eeeeeee eeeeeeeee eee ee eeeeeeeeee eeee, eeeeeeeeee eeee eeeeeeee eeeeeeee eee eeeeee 8.8 eeeeeeeeeee ee eeeeeee. Meeeeee, ee ee eeeeeeee ee eeeeeee eeeeeeeee ee eee eee ee eee eeeeeeee eee eeeeeee-eeeeeeeee eeeeeeeee eeee eeee eee eeeeeee ee eeee eeeeeeee. Meeeeee eeee eeeeeeeeeeeee, eeee eeeeeeeeeeeeeee eeeeeee eeee eeeeeeee ee e eeeeeeeeee eeeeeee. Meeeeee, eee eeeee eeeeee eeeeee ee eeeeeeeeee ee eeeeeee eeee eeee eeeeeeeeeeee eeeeeeee eeeeeeeeee eeee eeeee eeeeeeeee ee eeeeeeee ee eeeeee eee eeee eeeeeee.
Mee eeeeeeeeeeee eeeeeeee, e eeeeeee eeeeeee-eeeeeeeee B-eeeeeeeeeeeeeeeee eeeeeeeee eeeee, eeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeeeeeeee, ee eeeee ee Meeeee 8.
Meeeee 8 Meeeeee Meeeeee-Meeeeeeee Meeeeeeeeeeeeeee B-Meeeeeeeeeeeeeeee
References
eng_Latn eng_Latn eng_Latn knc_Latn eng_Latn eng_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn lit_Latn lit_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn bam_Latn lvs_Latn