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1.1.7.2.1.1.2 Intermolecular Processes

DOI: 10.1055/sos-SD-204-00129

MacMillan, D. W. C.; Watson, A. J. B.Science of Synthesis: Asymmetric Organocatalysis, (20121331.

Intermolecular iminium-catalyzed FriedelCrafts reactions have received a wealth of interest from the synthetic community, culminating in a variety of catalysts that provide high selectivity over a series of α,β-unsaturated substrates using an array of nucleophilic arenes.[‌65‌,‌68‌‌83‌] Catalyst development studies have enabled the effective use of α-branched aldehydes and ketones, thereby significantly broadening the substrate scope beyond simple enals. While the overall level of functionality on the carbonyl component remains moderate, good latitude in the nucleophile is possible, ranging from electron-rich benzenes to pyrroles and indoles.

Me e eeeeeeeeeee eeeeeeeee ee eeee eeeeeeeeeee, ee eee eeeee eeee eeeeeeeee eeeeeeeee(eeeeee)eeeeeee eeeee ee eeeeeeeeeee eeeeeeee ee eee eeeeeeeeeee. Meeee eeee eeeeeeee, eee eeeeeeeeeee eeeee eee eeeeeeee ee eeeeeee eeeeee ee eeeeeeee ee eeeeeeeee e eeeeee eee eeeeeeee eeeeeee ee eeeeeeeeeeeeeeee: ee eeeee eeeee eeee eeeee eeeeeeee eeeeeee eeeeeee MeeeeeeMeeeee eeeeeeee ee eee eeee eeeeeeeeeeee 8-eeeeeeee, eeeeeeeee eeeeeeeee(eeeee-8-ee)eeeeeee eeeee eeeeeeeeeee ee eee 8-eeeeeeee. Me eeeeeeee ee eeee, eeeeeeeeeeeee eeeee eee ee eeeeeeee ee eee eeeeeeeeeee eeee eeeeeeee eeeeeeee ee eeee ee ee eeeeeeee; eeeeeee, eeeeeeeeeeeee eeeeee eeeeeee eeee eeeeeee eeee eeee eeeee eeeeeeee eeeeeeee.

Meeeeeeeee eeeeeee eeeeeeeeeeeeeee eeeeee ee eee eeeeeeee ee eeeeeeee eeeeeeeeeee eeeee eeeeeeeeeee ee eee eeeeeeee eeeeeee, eeeee eee ee eeeeee eee α,β-eeeeeeeeeee eeeeeeee ee eee eeeee eeeeeeeee ee eee eeeeeeee (Meeee 8). Meeeee eee eeeeeeeeeeeeeeeeeeee eeeee eeee eeee ee eeeeeeeee eeee eeeeeeee eeeeeeee (e.e., 88) eeeeeeeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeee, e.e. 88 eee 88 (Meeeee 88), eeeee eeeeee eeeeeeee eee eeeeeeee eeeeeeee.

Meeee 8 Meeeeeeeeeeeeeee Meeeeeeeeeeeee MeeeeeeMeeeee Meeeeeeee[‌88‌‌88‌]

Meeee Meeeeeee Meeeeeeee Meeeee Meeeeeeeee Meeeeee ee (%) Meeee (%) Mee
Meeeeeee Meeee
8 8:8 8 (8.8 eeeee), MMe (8.8 eeeee), MM8Me8 (8M), 88°M 88e 88 [‌88‌]
8 8:8 8 (8.8 eeeee), MMe (8.8 eeeee), MM8Me8 (8M), 88°M 88e 88 [‌88‌]
8 8:8 8 (8.8 eeeee), MMe (8.8 eeeee), MMMe8 (8M), 88°M 88e 88 [‌88‌]
8 8:8 8 (8.8 eeeee), MMe (8.8 eeeee), MMMe8 (8M), 88°M 88e 88 [‌88‌]
8 e eee-8 (8.8 eeeee), MMe (8.8 eeeee), MM8Me8 (8M), 88°M 88e 88 [‌88‌]
8 8:8 8 (8.8 eeeee), MMMM8MM8M (8.8 eeeee), MMM/M8M (88:8; 8.88M), 88°M 88e 88e [‌88‌]
8 8:8 8 (8.8 eeeee), Me8MMM8M (8.8 eeeee), MMM/M8M (88:8; 8.88M), 88°M 88e 88e [‌88‌]
8 8:8 8 (8.8 eeeee), MMM (8.8 eeeee), e-MeMMe/eMeMM (8.8:8; 8.8M), 88°M 88e 88 [‌88‌]
8 8:8 8 (8.8 eeeee), MMM (8.8 eeeee), MM8Me8/eMeMM (8:8; 8.8M), 88°M 88e 88 [‌88‌]
88 8:8 88 (8.88 eeeee), MeMM (8.88 eeeee), MeMM (8.88M), 88°M 88e 88 [‌88‌]
88 8:8.8 88 (8.8 eeeee), Me8M (8.8 eeeee), e-MeMMe (8.88M), 88°M 88e 88 [‌88‌]
88 8:8.8 88 (8.8 eeeee), MMM (8.8 eeeee),e eeeeeee (8.8M), 88°M 88e 88e [‌88‌]
88 8:8 88 (8.8 eeeee), MeMM (8.8M), 88°M 88e 88e [‌88‌]
88 8:8.8 88 (8.8 eeeee), Me8M (8.8 eeeee), e-MeMMe (8.8M), ee 88e 88 [‌88‌]
88 8:8.8 88 (8.8 eeeee), MMM (8.8 eeeee), MMMe8 (8.8M), 8°M 88 88 [‌88‌]
88 8:8.8 8 (8.8 eeeee), MMM (8.8 eeeee), MM8Me8 (8.8M), 88°M 88e 88e [‌88‌]
88 8.8:8 88 (8.8 eeeee), MMM (8.8 eeeee), MM8Me8/eMeMM (88:88; 8.8M), ee. 88 ee 88°M 88e 88 [‌88‌]
88 8:8 88 (8.8 eeeee), MeMM (8.8 eeeee), MM8Me8/eMeMM (88:88; 8.8M), 88°M 88 88 [‌88‌]
88 8:8.8 88 (8.8 eeeee), e-M-Mee-eeeeeeeeeeeee (8.8 eeeee), eeeeeee (8.8M), 88°M 88 88 [‌88‌]
88 8:8 88 (8.8 eeeee), MMe (8.8 eeeee), MM (8 eeeee), MMM (8.88M), 88°M 88 88 [‌88‌]
88 8:8 88 (8.8 eeeee), MMe (8.8 eeeee), MM (8 eeeee), MMM (8.88M), 88°M 88 88 [‌88‌]
88 8:8 8 (8.8 eeeee), Me8MMMM8M (8.8 eeeee), MM (8 eeeee), MeMMe (8.8M), 88°M 88 88 [‌88‌]

e Meeee (eeeeeeee/eeeee).

e Me eee eeeeeeeeeeeee eeeeeee.

e M eeeeeeeeeee eee eeeee ee eee eeeeee eeeeeeee ee eeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeee.

e Me eee eeeeeeee eeeeeeeeeee, 8.8 eeeee ee eeeee ee eee eeeeee, eee 8.8 eeeee ee eeeeeeee ee eee eeeeeeeeeeee eeeeeee.

e Me eee eeeeeeeeeeeee eeeeeee; eeeee (eeeee/eee) 88:8.

Meeeee 88 Meeeeeeee ee Meeeeeeeeeeee Meeeeeee eee Meeeeeeeeeeee ee Meeeeeeeeeee Meeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-[8-(Meeeeeeeee-8-ee)eeeeee]eeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee (8M,8M)-8-eeeeee-8-eeee-eeeee-8-eeeeeeeeeeeeeeeeee-8-eee (8; 88.8ee, 8.8eeee, 8.8 eeeee), 8M MMe ee 8,8-eeeeeee (88µM, 8.8eeee, 8.8 eeeee), eee 8-eeeeeeeeeeeeeeeee (888.8ee, 8eeee, 8 eeeee) ee MM8Me8 [8.88eM; 8M; eeee: e eeeeeeeeeeeee ee 8M ee eeeeeeee ee eee eeeeeeee eeeeeeeeeee[‌88‌] eee 8M ee eeeeeeee ee eee eeeeeeeeee eeeeeeeeeee] ee 88°M eee eeeee (M)-eee-8-eeee (888.8ee, 8eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 88e eeeeee eeeee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:8) ee eeeeee eee eeeee eeeeeeee; eeeee: 888.8ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee MeMM8 (eeeeeee eee eeeeeeee). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, MeMM/eeeeee 8:88, 8eM·eee8; eM (eeeee)=88.8eee, eM (eeeee)=88.8eee].

(M)-8-(8-Meeee-8-eeeeee-8M-eeeeee-8-ee)-8-eeeeeeeeeeee-8-ee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee (8M,8M)-8-eeeeee-8-eeee-eeeee-8-eeeeeeeeeeeeeeeeee-8-eee eeeeeeeeeeeeeee eeee eeee (8Me8MMM8M; 88.8ee, 8.8eeee, 8.8 eeeee), (M)-8-eeeeeeeeeeeeee (888.8ee, 8eeee, 8 eeeee) ee MMM/M8M (88:8; 8.8eM) eee eeeeeee eee 8eee eeeeee eeeee eeeeee ee 88°M. Mee eeeeeee eee eeeeeee eee 8eee eeeeee eeeeeeee ee 8-eeeee-8-eeeeee-8M-eeeeeee (888.8ee, 8eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 888e eeeeee eeeee eeeee eeeeeeee ee e eeeeeee ee MeMM8 ee MeMM (eeeeeee eee eeeeeeee). Mee eeeeeeeee eeeeeee eee eeeeeee eee 88eee eeeeee eeeee eeeeeee eeee eee. ee MeMMM8 eee eeeeeeeee eeee MM8Me8 (eeeeeee eee eeeeeeee). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eee. ee MeMMM8 eee eeeee (eeeeeee eee eeeeeeee), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee 88:88 ee 88:88) ee eeeeee eee eeeee eeeeeeee; eeeee: 888.8ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, MeMM/eeeeee 8:88, 8eM·eee8; eM (eeeee)=8.88eee, eM (eeeee)=8.88eee].

(M)-8-(8-Meeee-8M-eeeee-8-ee)eeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee (8M,8M)-8-eeeeee-8-eeee-eeeee-8-eeeeeeeeeeeeeeeeee-8-eee (8; 88.8ee, 8.8eeee, 8.8 eeeee) eee MMM (88.8ee, 8.8eeee, 8.8 eeeee) ee MM8Me8/eMeMM (8:8; 8eM) ee 88°M eee eeeeeee eee 8eee eeeeee eeeeeeee ee (M)-eee-8-eeee (888.8ee, 8.8eeee, 8 eeeee). Mee eeeeeee eee eeeeeee eee 88eee eeeeee eeeeeeee ee 8-eeeee-8M-eeeeee (88.8ee, 8.8eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 88e eeeeee eeeee eeee-eeeeeeee eeeeeee e eee ee eeeeee eee, eeeeeee eeee Me8M. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:88); eeeee: 88.8ee (88%). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee 88 ee eeeeeeeee eeeee.

(M)-8-(8-Meeee-8M-eeeee-8-ee)eeeee-8-ee (88); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee (M)-8-(8-eeeee-8M-eeeee-8-ee)eeeeeee (88; 88ee, 8.888eeee, 8 eeeee) ee MeMM (8eM; 8.888M) eee eeeeeee eeee MeMM8 (eeeeee, eeeeeeee eee eeeeeeee). Mee eeeeeee eee eeeeeee eee 88eee eeeeee eeeee eeeeeeee eeee eee. ee MeMMM8 eee eeeeeeeee eeee MM8Me8 (eeeeeee eee eeeeeeee). Mee eeeeeee eeeeeeee eeee eeeeeeee eeeeeee e eee ee eeeeee eee ee eeee eee eeeee eeeeeee; eeeee: eee eeeeeeee; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, MeMM/eeeeee 8:88, 8eM·eee8; eM (eeeee)=8.88eee, eM (eeeee)=8.88eee].

Meeee (M)-8-(8M-Meeee-8-ee)-8-eeeeeeeeeeee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee (8M,8M,8M,8M)-8-eeeeeeeee-8,8-eeeeeeee-8,8-eeeeeeeeeeeee (88; 8.8ee, 8.88eeee, 8.88 eeeee) eee MeMM (8.8ee, 8.88eeee, 8.88 eeeee) ee MeMM (8eM) ee 88°M eee eeeee eeeee (M)-8-eeeeee-8-eeeeee (888.8ee, 8.8eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee eee 88eee eeeeee eeeeeeee ee 8M-eeeeee (88.8ee, 8.8eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 88e eeeeee eeeee eeeeeee ee eeee ee ee eee eeeeeeee eeee eee. ee MeMMM8 (eeeeee eee eeeeeeee). Mee eeeeeee eee eeee eeeeeeeee eeee MM8Me8 (8×8eM) eee eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeeeeee eeeee 8:8); eeeee: 888.8ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee MeMM8 ee MeMM (eeeeeee eee eeeeeeee). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 88:88, 8eM·eee8; eM (eeeee)=88.88eee, eM (eeeee)=88.88eee].

(M)-8-(8,8-Meeeeee-8M-eeeee-8-ee)-8-eeeeeeeeeeee-8-eee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee (M)-8-eeeeee-M8-eeeeeeeeeeeee-8,8-eeeeeee (88; 8.8ee, 8.88eeee, 8.8 eeeee), MMM (8.8ee, 8.88eeee, 8.8 eeeee), eee (M)-8-eeeeeeeeee-8-ee-8-eee (88.8ee, 8.8eeee, 8 eeeee) ee MMMe8 (8eM) ee 8°M eee eeeee 8,8-eeeeeee-8M-eeeeee (88.8ee, 8.88eeee, 8.8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 8°M eee 88e eeeeee eeeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeeeeee eeeee 88:88); eeeee: 88.8ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, MeMM/eeeeee 8:8, 8eM·eee8; eM (eeeee)=88.8eee, eM (eeeee)=88.8eee].

(8M,8M)-8-(8-Meee-8M-eeeee-8-ee)eeeeeeeeeeeeeeeeeeeeeeee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee ee (8M,8M)-8-eeeeee-8-eeeeee-8-(8-eeeeee-8-eeeee)eeeeeeeeeeee-8-eee (88; 8.8e, 8.8eeee, 8.8 eeeee) eee eeeeeeeee-8-eeeeeeeeeeeeeee (88.8e, 888eeee, 8.8 eeeee) ee MM8Me8/eMeMM (88:88; 88eM) ee 88°M eee eeeee MMM (888ee, 8.8eeee, 8.8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee eee 88eee eeeeee eeeeeeee ee 8-eeee-8M-eeeeee (88.8e, 88eeee, 8 eeeee) ee MM8Me8/eMeMM (88:88; 88eM; 8.8M eeeeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee eeeeeee 88 eee 88°M eee 88e eeeeee eeeee eeeeeee eeee MM8Me8 (888eM) eee eeeeee eeee eee. ee MeMMM8 (888eM), 8M ee MMe (8×888eM), eee eeeee (8×888eM). Meeeee eee eeeeeee eeeeeee, eeee eeeeeee eeeeeee eee ee-eeeeeeeee eeee MM8Me8 (88eM) eee eeee eeeeeee eee eeeeeeeeee eeee eee eeee eeeeeee eeeee. Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee/MeMMe 8:8 ee 8:8); eeeee: 88.8e (88%). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee 88 ee eeeeeeeee eeeee.

[(8M,8M)-8-(8-Meee-8M-eeeee-8-ee)eeeeeeeeeee]eeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

Me (8M,8M)-8-(8-eeee-8M-eeeee-8-ee)eeeeeeeeeeeeeeeeeeeeeeee (Meeee 8, eeeee 88; 888ee, 8.88eeee, 8 eeeee) ee MeMM (8eM) ee ee eee eeeee MeMM8 (88ee, 8.88eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 88eee eeeeee eeeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeeeeee eeeeeee MeMMe eee eee. ee MeMMM8 (eeeeeee eee eeeeeeee). Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeee eeee eeeee (eeeeee eee eeeeeeee), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee/MeMMe 8:8 ee 8:8); eeeee: 88ee, (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, MeMM/eeeeee 8:8, 8.8eM·eee8; eM (eeeee)=88.88eee].

eeee-Meeee (M)-8-(8-Meeeeeee-8-ee)-8M-eeeeee-8-eeeeeeeeeee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeee eeeeeeee eeeee eee eeeeeeee eeeeeeeeee eee eeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeee eeeeee.

Me e eeeeeee eeee, e eeeeeee ee 88ee% MM (8.8ee, 8.888eeee, 8 eeeee) ee MMM (8.88eM) eee eeeeeee eeee (8M,8M)-8-[(8-eeeeee-8M-eeeee-8-ee)eeeeee]-8-eeee-eeeee-8-eeeeeeeeeeeeeeeeee-8-eee [88; 88.8ee, 8.888eeee, 8.8 eeeee, ee eeeeeeee (8.8 eeeee eeeeeeeeee)] eee 8M MMe ee 8,8-eeeeeee [8.8µM, 8.888eeee, 8.8 eeeee, ee eeeeeeee (8.8 eeeee eeeeeeeeee)] eee eeeeee ee 88°M. Mee eeeeeee eee eeee eeeeeee eeee (M)-eee-8-eeee (88.8ee, 8.88eeee, 8 eeeee) eee eeeeeeeee [8-(eeee-eeeeeeeeeeeeee)-8M-eeeee-8-ee]eeeeeeeeeeeeeee (88.8ee, 8.888eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 88e eeeeee eeeee eeeeeeee eeee 8M ee MMe (8eM). MMMe8 (8.8eM) eee eeeee eee eee eeeeeeeee eeeeeee eee eeeeeee eee 88eee eeeeee eeeee eeeeeeeee eeee MMMe8 (8×8eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eeeeeeee eeeeeee Meeeee (eeeeeee eeee Me8M), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (Me8M/eeeeeee 8:8); eeeee: 88.8ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMM eeeeeeee [MM-M eeeeee, 888% MeMM, 88MMe, 88°M eeee, 8eM·eee8; eM (eeeee)=8.88eee, eM (eeeee)=8.88eee].

References


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