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2.3.6.3.1 Cooperative Catalysis of Brønsted Acids with Transition-Metal Complexes

DOI: 10.1055/sos-SD-205-00523

Han, Z. -Y.; Wang, C.; Gong, L. -Z.Science of Synthesis: Asymmetric Organocatalysis, (20122713.

A mechanistically real cooperative catalysis using a Brønsted acid/transition-metal complex binary system was first reported in 2006.[‌51‌] In the reductive coupling of 1-phenylbut-3-en-1-yne (40) with pyridine-2-carbaldehyde catalyzed by an achiral rhodium complex, the presence of chiral phosphoric acid 39 leads to the generation of the product with substantial levels of enantiopurity (Scheme 22). The high asymmetric induction results from the Brønsted acid activating the aldehyde by protonation of the pyridine moiety, thereby forming a chiral intermediate capable of controlling the subsequent reductive CC bond-forming reaction.

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

Mee eeeeeeee eeeeeee ee eee eeeeeeeeeee eeeeeeeee eee eeee eeeeeeeeeeee ee eee eeeeeeeeeeeeeeee eeeeeeeeeeee ee eeeeee. Me eeeeeeeeeeeeeeee eeeeeeee ee eeeeeeee eeeeeee 88 ee eeeee eeeeee (e.e., 88) eee eeee eeeeeeeeeeee ee eeeeeeeee ee eeeeeee eeeeee eeee ee eeeeeeeeeee eeee eeeeee eeeeeeeeee eeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeee eeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeeeee eee eeeee β,γ-eeeeeee α-eeeee eeeeee 88 ee eeee eeeee. Mee eeeeeee eeeeee eeee eeeeeeeee eee eeeeeeee eeeeee eeeeeee eee eeeeee eeeeeeeeee eeee eeeeeeeee eee α-eeeee eeeee eee eeeeeeee eee eeeeeeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeeeee, ee eeeeeeeeeee eeeeeeeeeee eeeee eeeeeee e eeeeee eeeeee eeeeeeeee eeeeeee eeeeeeeee eeee e eeeeeeeeee-eeeeeeee eeeeeeee eeee eeeee ee eeeeeeeeeee eee eeeeeeeee eee eeeeeeeeee eeeeeeeee ee eee eeeeeeeeeeeeee.

Meeeee 88 Meeeeeeeee Meeeeeeeeeee ee ee α-Meeee Meeee[‌88‌]

Meeeeeeeeee 88

M8 ee (%) Meeee (%) Mee
Me 88 88 [‌88‌]
8-Mee 88 88 [‌88‌]
8-MeMM8M8 88 88 [‌88‌]
8,8-(MeM)8M8M8 88 88 [‌88‌]
8-e-MeM8M8 88 88 [‌88‌]
8-Me(MM8)8M8M8 88 88 [‌88‌]
88 88 [‌88‌]
88 88 [‌88‌]

Meeeee 88 Meeeeeee Meeeeeeee eee Meøeeeee Meee Meeeee(M) Meeeeee Meeeeeeee Meeeeeeeeeee ee α-Meeee Meeeee[‌88‌]

Meee eeeeeeee, eeeeeeeeee eeeeeeeeeeee ee eeeeee eee eeee eeeeeeee eeeee eeee eee eeeeeeee eeeeeeeeeee eeeeeeeee eeeeeee.[‌88‌] Me eeee eeee, eeeeeeeee eeeee eeeee eee eeee ee Meøeeeee eeeee ee eeeeeeee eeeeee eeeeeee eeeeeeee eeeeeee ee eeeeeeeeeee eeee e eeeeee eeeeeee ee eeeeeeee eee eeeeeee, ee eeeeeeeeeee ee Meeeee 88. Meeeeeeeeeeee, eeee eee eeeee eeee eee eeeeee eeeeeee eee ee eeeee ee eeeeeeeeeee eee eeeeeeeeee eee eeeeeeeeeee ee eeeeee eeee eeeeeeeeee eeeeeeeee. Meee eeeeeeeeeeeee, eeee eeeeeeee eeeeeeeee e eeeee eeeee ee eeeee eeeeeeeeee eeeeeeeee eeee eeeeeeee eeeeee eeeeeeeee ee eeeeeeeeee eeee eeee eeeeeeeee ee eee eeeeeeee eeeeeeeeee eeee eee eeeeee eeeeeee,[‌88‌] eeeeeee eeee eeeeeeee α-eeeee eeeeee eee ee eeeeeeeeeeee. Me eeeeeeee, eeee eeeee- eee eeee-eeeeeeeeeee eeeeeee 88 eee eeeeeeee eeeeeeeeeeee eeeeeeeeee eeeeee eeeeee 88 eeee eeeee eeeeeeeeee 88 (Meeeee 88).

Meeeee 88 Meeeeeeeee Meee[‌88‌]

Meeeee 88 Meeeeeeeee Meeeeeeeeeee ee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeeeeeee Meeeee ee (%) Meeee (%) Mee
Me Me Me (8-Mee)8M 88 88 [‌88‌]
Me 8-MeM8M8 Me (8-Mee)8M 88 88 [‌88‌]
8-M8MM8M8 8-Mee Me (8-Mee)8M 88 88 [‌88‌]
8-MeM8M8 8-Mee Me (8-Mee)8M 88 88 [‌88‌]
Me 8-MeM8M8 Me (8-Mee)8M 88 88 [‌88‌]
8-MMM8M8 8-Mee Me (8-Mee)8M 88 88 [‌88‌]
Me 8-Mee Me Me8M 88e 88 [‌88‌]
MMM e-Me Me (8-eeeeeeee)8M 88 88 [‌88‌]
Me 8-Mee MMM (8-eeeeeeee)8M 88e 88 [‌88‌]
Me 8-Mee MM8MMe (8-eeeeeeee)8M 88 88 [‌88‌]
Me 8-Mee Me (8-eeeeeeee)8M 88 88 [‌88‌]
MMM Me Me (8-eeeeeeee)8M 88 88 [‌88‌]

e Me ee.

M eeeeeeeee/Meøeeeee eeee eeeeeeeee eeeeeeeeee α-eeeeeeeeee ee α-eeeeeeee eeeeeeeee 88 eeee eeeeeeeee eeeeeeeeeee 88 eee eeee eeeeeeeee eeeeeeeee α-eeeeeeeee eeeeeeeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeeeee eeee eeeeeeeeeee eee eeeeeeeeeeee ee eee eeeeeeeee eeeee eeee eee eeeeeeee ee eeeeeeee eeeeeeeeee eeeeeeeee eeee 88. Meeeeeeee eeeeeeee ee eeeeeeeee ee 88 eeeeeeeee π-eeeeeeeeeeeeee eeeeeeeeeeee 88, eeeee eeeeeeeee ee eeeeeeeeeeeeeeee eeeeeee eeeeeeeeee ee eeeeeee eee eeeeeee. Mee eeeeeeeeee eeee ee eeeeeeee ee eeee e eeee eeeeeeeee eeee eeeeeeeee eee eeeeeeeeeee ee eeeee ee eeeeeeeeee eee eeeeeeee ee eee MM eeee eee eee eeeeeeeee ee eee eeeeeeeeeeeeee eeeeeee eee eee eeeeeeeee eeeeeeeee eeee eeeeeeeee ee eee eeeeeeeeeeee/eeeeee eee eee eeeeeeee π-eeeeeeeeeeeeee eeeeeeeeeeee 88 ee eeeeee eeeeeeeee (Meeeee 88). Meee eeeeeeee eeeeeeee ee eeeeeeee ee eee-eeeeee eeeeeeeeeee eeeeeee eee eeeeeeeee eeeeeeeeeeeeeeee eeeeeeeeee ee eeeeeeeee.

Meeeee 88 Meeeeeeeee α-Meeeeeeeee ee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 ee (%) Meeee (%) Mee
Me Me M 88 88 [‌88‌]
Me 8-Mee M 88 88 [‌88‌]
Me 8-Mee M 88 88 [‌88‌]
Me 8-MM8M8 M 88 88 [‌88‌]
Me 8-MM8M8 M 88 88 [‌88‌]
Me 8-eMeM8M8 M 88 88 [‌88‌]
Me 8-eeeeeeee M 88 88 [‌88‌]
Me 8-eeeeeee M 88 88 [‌88‌]
M 88 88 [‌88‌]
Me Me M 88 88 [‌88‌]
Me Me Me 88 88 [‌88‌]
Me Me Me 88 88 [‌88‌]

Meeeee 88 Meeeeeee Meeeeeeee ee α-Meeeeeeeee ee Meeeeeeee[‌88‌]

Mee eeeeeeeeeee eeeeeeeee ee e eeeeeeeeee eeee eee e eeeeeee eeeeeee eee eeee eeeeeeeeeeee eeeeeee ee e eeeeeeeeeeeeee eeeeeeee.[‌88‌] Mee eeeee-eeeeeeeee eeeeeeee ee eeeeeeeeeeeee 88, eeeeeeee (e.e., 88), eee eeeeeeeee 88 ee eeeeeeeee ee eee eeeeeeeeeee ee eeeeeeeee(MM) eeeeeeeeeeee eee eeeeee eeeeeeeeee eeee 88 eee eeeeeeee eeeeeeee ee eeeee eeeeee β-eeeee-α-eeeeeee eeee eeeeeeeeeee 88 eeee eeeeeeeee eeeeeeeee- eee eeeeeeeeeeeeeeeeeeee (Meeeee 88). Mee eeeeeee eeeee 88 eeeeee ee eeee eeee e eeeeeeeeeeee eee ee eeeeeee eeeeeeeee ee e eeeeeee eeeeeee eeeeeeeee eee eeeeeeeeeeeeeeee Meeeeee-eeee eeeeeeee eeee ee eeeee eeeeeeeeeeeeee eeeeeeeee ee e eeeeee eeeeeeeeee eeee eee eeeeeeee eeeeeeeeee eeeee 88 ee eeeeeeee eeeeeeeeeeeeeee eeeeeee (Meeeee 88). Meeeeeeeeee, eee eeeeeeee eee eeee eeeeeeeeeeee eeeeeeee ee e eeee-eeeeeeeee eeeeeeee,[‌88‌] eeeee eeeeeeee, eeeeee, eeeeeeeee, eee eeeeeeeeeeeee, ee eeeee eee eeeeee eee eeeeee eeee eeeeee eee eeeeeeeee eeeee eeeeeeeee ee eee Meøeeeee eeee.

Meeeee 88 Meeeeeeeee Meeee-Meeeeeeee Meeeeeee ee Meeeeee eee Meeee Meeeeeeee eeee Meeeee[‌88‌]

Meeeeeeeeee 88

Me8 Me8 ee ee (%) Meeee (%) Mee
Me Me >88:8 88 88 [‌88‌]
Me 8-Mee >88:8 88 88 [‌88‌]
Me 8,8-Me8M8M8 >88:8 88 88 [‌88‌]
Me 8-Mee >88:8 88 88 [‌88‌]
Me 8-Mee >88:8 88 88 [‌88‌]
Me 8-MeM8M8 >88:8 88 88 [‌88‌]
Me 8-MeM8M8 >88:8 88 88 [‌88‌]
Me 8-MeM8M8 >88:8 88 88 [‌88‌]
Me 8-eeeeeeee >88:8 88 88 [‌88‌]
8-MeMM8M8 Me >88:8 >88 88 [‌88‌]
8-MeMM8M8 8-MeM8M8 >88:8 88 88 [‌88‌]
8-MeM8M8 Me >88:8 88 88 [‌88‌]
8-MeM8M8 8-MeM8M8 >88:8 88 88 [‌88‌]
8-MeM8M8 8-MeM8M8 >88:8 88 88 [‌88‌]
8-MeMM8M8 Me 88:8 88 88 [‌88‌]

Meeeee 88 Meeeeeee Meeeeeeee ee eee Meeee-Meeeeeeee Meeeeeee[‌88‌]

Me eeeeeeeeee eeeeeeeeeeeee ee eeeeeee eeeeee eeee ee eeeeeeeeeeeee eeeeeeeee ee ee eeeeeee(MMM) eeeeeee eee e Meøeeeee eeee eee eeee eeeeeeee.[‌88‌] Mee eeeeeee eeeeeeee 88, eeeeee eeeeeeeee ee eeee ee eeeeeeeee ee eeeeeeeeeee ee eee eeeeeeee eeeeeeee 88 eeee e eeeeee Meøeeeee eeee, eeeeeee eeeeeeeeeeee eeeeeeeeeee eee eeeeeeeee eeeeeeeeeeeeeeeeeeee. Meeeeeeeee, eee eeeeeeeeee eeeeeeeeeeee eeeeeeeee eeee ee eeeeeeeeee Meøeeeee eeee ee eeee. Mee eeeeeeeeee eeee eeeee eee eeeee ee eee eeeeeeeeeeeee eeeeeeee eeeeeeeee eeeeeeeeee ee eee eeeeeeee eeeeeeee 88 ee eeeeeeee ee eeeeee eeeeeee eeee e eeeeee eeeeeeeee eeeee ee eeeeee eeee eeeeeeeeeeeeeeeee eee eeeeeeeeee ee eeeeee eeeeeee ee eeee eeeeeeeeee. Me eee eeeeeeee ee 8eee% ee eeeeeee eeeeeeee 88 eee 8eee% ee eeeeee eeeeeeeeee eeee 88, eee eeeeeeee eeeeeeeeeeeee ee eeeeeee eeeeee 88 eeeeeeee eeeeee eeeeee 88 ee eeeeeeeee eeeeee eee eeeeeeeeeeeeeeeeeeee (Meeeee 88). Mee eeeeeeee eee eeee eeeeeee eeeeeeee ee e eeeeeeeee eeeeeeeee ee eeeeeee ee eeeee eee Meøeeeee eeee ee eee eeee e eeeeeeeeee, eee eeee eeeeeeeeeee eee eeeee eeeeeeeee.[‌88‌,‌88‌]

Meeeee 88 Meeeeeeeee Meeeeeeeeeeee ee Meeeeee Meeeee[‌88‌]

Meeeeeeeeee 88

M8 Me8 ee (%) Meeee (%) Mee
Me 8-MeMM8M8 88 88 [‌88‌]
8-Mee 8-MeMM8M8 88 88 [‌88‌]
8-Mee 8-MeMM8M8 88 88 [‌88‌]
8-MeM8M8 8-MeMM8M8 88 88 [‌88‌]
8-MeM8M8 8-MeMM8M8 88 88 [‌88‌]
8-MeMM8M8 8-MeMM8M8 88 88 [‌88‌]
8,8-(MeM)8M8M8 8-MeMM8M8 88 88 [‌88‌]
8-MMM8M8 8-MeMM8M8 88 88 [‌88‌]
8-M8MM8M8 8-MeMM8M8 88 88 [‌88‌]
8-M8MM8M8 8-MeMM8M8 88 88 [‌88‌]
8-eeeeeeee 8-MeMM8M8 88 88 [‌88‌]
Me 8-MeM8M8 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
8-MeMM8M8 Me 88 88 [‌88‌]
8-eeeeeeee Me 88 88 [‌88‌]
eMe 8-MeMM8M8 88 88 [‌88‌]
(MM8)8Me 8-MeMM8M8 88 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee (8M)-8-[(8-Meeeeeeeeeeee)eeeee]-8-eeeeeeeee-8-eeeeee (88, M8=Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeee [(8-eeeeeeeeeeeee)eeeee]eeeeeee (88; 88.8ee, 8.888eeee), eeeeeeeeee eeee 88 (8.8888eeee, 88eee%), MeMMe (8.88888eeee, 8eee%), eee eeeeeeeeeeeeeee (88, M8=Me; 8.888eeee, 8 eeeee) eeee eeeeeeeee ee eeeeeee (8eM) ee e eeeee-eeeeee eeee. Meeee eee eeeeeee eee eeeeeee ee 88°M eee 8888e, eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee) ee eeeeee eee eeee eeeeeee; eeeee: 88.8ee (88%); 88% ee.

M-[(8M)-8,8-Meeeeeeeeeee-8-ee-8-ee]eeeeeee (88, M8=M8=M8=Me); Meeeeee Meeeeeeee:[‌88‌]

Me(MMMe)8MM8 (8.88ee, 8.8888eeee), (M)-M-(eeee-eeeeeeeeeeeeee)eeeeeee (8.8ee, 8.888eeee), (8-Mee)8M (8.8ee, 8.8888eeee), eeeee 88 (M8=M8=Me; 8.88eeee), eee eeeeeeeeeeeeeee (88, M8=Me; 8.88eeee) eeee eeeeeeeee ee MM8Me8 (8.8eM). Meeee eeeeeeee ee 8°M eee 88e, eee eeee eee eeeeeeee eeeeeee e eeeee eeeeee (eeeeee eee, MM8Me8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee); eeeee: 88.8ee (88%); 88% ee.

(8M)-8-Meeeee-8-eeeeeeeeee-8-eeee (88, M8=Me; M8=Me; M8=M); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee-eeeee Meeeeee eeee eeeeeee eeee eeeeeeeee 8-Å eeeeeeeee eeeeee eee e eeeeeeee eeeeeee eee, eeee eeeee Me(MMe8)8 (88ee, 8.88eeee) eee eeeeee eeeeeeeeee eeee eeeeeeee 88 (8.8ee, 8.888eeee) eeeee e eeeeeeee eeeee eeeeeeee. M eeee ee 8-eeeeeeeeeeeeee (88, M8=Me; M8=Me; 8.88eeee) eee eeeee eeeeeee 88 (M8=M; 8.88eeee) ee eeeee e-MeMMe (8.88eM) eee eeeee eee eee eeeeeeeee eeeeeeeeee eee eeeeeee ee 88°M eeeee eeeee. Meee eeeeeeeeee ee eee eeeeeeee (eeeeeeeee ee MM/MM), eee eeeeeee eee eeeeeee eeee Me8M (8eM). 8M MMe (8eM) eee eeeee eee eee eeeeeee eee eeeeeee eeeeeeeeee eee 88eee. Mee eeeeeee eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeee eee eeeee eeeeeee. Meeeeeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeeeee eeeeeeee eee eeee eeeeeee; eeeee: 88.8ee (88%); 88% ee.

Meeeee (8M,8M)-8-(8-Meeeeeeeeeeeee)-8-[(8-eeeeeeeeeeeee)eeeee]-8,8-eeeeeeeeeeeeeeeeee (88, Me8=Me8=Me); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee Me8(MMe)8 (8.888eeee), eeeeee eeeeeeeeee eeee 88 (8.888eeee), eeeeeee 88 (8.88eeee), eeeee 88 (Me8=Me; 8.888eeee), eee 8-Å eeeeeeeee eeeeee (8.8e) ee MM8Me8 (8eM) eeeee ee eeeee eeeeeeeeee eee eeeeee eeee ee 88°M. Meeeee eeeee(eeeeee)eeeeeee (88, Me8=Me; 8.88eeee) ee MM8Me8 (8eM) eee eeee eeeee eeee 8e eee e eeeeeee eeee. Meeee eeeeeeeeee ee eee eeeeeeee, eee eeeeeee eee eeeeeee eee eeeeeeeeee 8e eee eee. ee MeMMM8 (8.8 eM) eee eeeee ee eeeeee eee eeeeeeee. Mee eeeeeee eee eeeeeee ee eeee eee eeeee eeeeeee, eeeee eee eeeeeeeee ee 8MMMM eeeeeeeeeeeee eeeeeeee eee eee eeeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee 8:88 ee ~8:88) ee eeee eee eeee eeeeeee; eeeee: 888.8ee (88%).

8-Meeeeee-M-[(8M)-8-eeeeeeeeeee]eeeeeee (88, M8=Me; Me8=8-MeMM8M8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee eeeee eeeeeee eeee eeeeee eeeeeeeeee eeee 88 (8ee, 8.888eeee) eee eeeee 88 (M8=Me; Me8=8-MeMM8M8; 8.8eeee) eee eeeee eeeeeee (8eM). Meeee eeeeeeee eee 8.8eee, Me eeeeeeee 88 (8ee, 8.888eeee) eee eeeeeeeeee. Mee eeeee eeeee eee eeee eeeeee eeee ee eeeeeeeee eeeeeeee ee eeeeeeeee eeee M8 (8×). Meeeeeeeeeeee eee eeeeeee eee ee 8MMe M8 eeee eeeeeeee ee 88°M eee 8888e. Mee M8(e) eee eeee eeeeeeeee eeeeeeee, eee eee eeee eee eeeeeeeeeee ee e eeeee eee eeeeeeeeeeee ee eeeeee eee eeeee eeeeeee. Meeeeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 88:8 ee 8:8) eeeeeeeee eee eeeeeee; eeeee: 888ee (88%); 88% ee.

References


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