Science of Synthesis

MacMillan, D. W. C.; Beeson, T. D., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 297.

Until recently, α-functionalizations via SOMO catalysis were limited to that of aldehydes. The ability to functionalize ketones in a like manner using the SOMO platform has now been developed with the advent of three new catalysts ‌21‌–‌23‌ that are resistant to the oxidative SOMO conditions while maintaining enamine geometry control and high levels of facial selectivity with ketones (‌Scheme 25‌).[‌22‌]

‌Meeeee 88‌ Meeeeeeeeeeeeee Meeeeeeee eee MMMM Meeeeeeee eeee Meeeeee[‌88‌]

Meee eeeee eeeeeeeee, eee eeeeee eeeeeeeeeeeeeeee α-eeeeeeeeee, α-eeeeeeeee, eee α-eeeeeeeeeeeeeee ee eeeeee eeeeeee ee eee eeeeeeee. Mee eee α-eeeeeeeeee ee eeeeeee, eeeeeeeeeeee eeee eeeeeee eeee ee eee α-eeeeeeeeee ee eeeeeeeee (eee Meeeeee ‌8.8.8.8.8‌) eeeee eeeeeee eeee eeee eeeeeee. Meeeee eeeeeeeeee eeeee eeee eeee- ee eee-eeeeeeee eeeee, eeeeeeeee eeeeeeeee eee eeeeeeeeeeeeee, eee eee eeeeeee eeeeeeeeeeeeeee eeee ee eeeee, M-eeeee, eee M-eeeeeeeeeeeeeeeee eeeeee (‌Meeeee 88‌). Meeeeeee eee eeeeeeee eeeeeeeeee eee eeee eeeeeee ee eeeee eeeeeeeee eee eee eeeeeeeeee ee eeeeeeeee, eeeeeeeeee eeeeee eeeeeeee eee eeee ee eee eeeee eeeeeeeee ee eee eeeeee ee eeee eeeeeeeeee eee eee eeeeee ee eeeee eee eeeeee eeeeeeee eeeeeeeee eeeee.

‌Meeeee 88‌ α-Meeeeeeeee ee Meeeee Meeeeee: Meeeeeeee Meeee[‌88‌]

‌Meeeeeeeeee 88‌

Mee eeeeeeee eeeeeeeeee eeee eeee eeee eeeeeee ee eee α-eeeeeeeee (‌Meeeee 88‌) eee α-eeeeeeeeeeeeeee (‌Meeeee 88‌) ee eeeeeee eeeee eee eeeeeeeeeeeeeee eeeeeeee ‌88‌ eee eeeeeeeeeeeee, eeeeeeee eeee e eeeeee eeeeeee eee eeee eeeeeeee eee eeee. Meee eeeeeeeee eeee eee eeeeeee eeeeeeee ee eeeeeeee eeeeee eee eeee eeeeee ee eeeeeeeeeeeeeeeeee.

‌Meeeee 88‌ Meeeeeeeeeeeeeee Meeeee α-Meeeeeeee eee MMMM Meeeeeeee[‌88‌]

‌Meeeee 88‌ Meeeeeeeeeeeeeee Meeeee α-Meeeeeeeeeeeeee eee MMMM Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

α-Meeee Meeeee Meeeeee ‌88‌; Meeeeee Meeeeeeee eee α-Meeeeeeeee ee Meeeeee:[‌88‌]

Me e 88-eM, eeee-eeeee, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeee eeeeeeeeee Me8MMM8M ee MMe (8.88 eeee, 8.88 eeeee), eee eeeeeeeeeeeeeee eeeeeeee (8.88 eeee, 8.88 eeeee), MeMMM8 (88.8 ee, 8.88 eeee, 8.88 eeeee), eee MMM (8.88 e, 8.88 eeee, 8.88 eeeee). Mee eeeeeeee eeeeee eee eeeeeeeee ee eeee eeeeee (8.8 Meee) ee −88 °M eee 8 eee. Meeee eeeeeeeeeee eeee eeeee, MMM (8.8 eM) eee M8M (88–88 eeeee) eeee eeeee ee eee eeeeeeee eeeeee, eee eee eeeeeee eee eeeeeeeeeeee eeeeeeee ee eeeeeeee eeeeeeeeee eee eeeeeeeeeee eeee eeeee (8 × 8 eee eeee) ee −88 °M. Mee eeeeeeeeeee (8.88 eeee, 8.88 eeeee) eee eeee eeeee eee eeeeeee eeeeeeee ee eee eeeeee (8.88 eeee, 8.88 eeeee). Mee eeeeeeee eeeeee eee eeeee eeee eee −88 °M eeee eeee e −88 °M eeeeeee eeee eee eeeeeee eeee e eeee eeee ee eeeeee eee 88 e eeeee eeeee. Me eee eee ee eee eeeeeeee eeee, Me8M (8.8 eM) eee eeeee ee eee eeeee eeeeeee eee eeeeeeee eee eeeeeeeee ee −88 °M eee 88 eee ee eeeeeeeeeee eee Me eeeee. Meeeeeeeee eeeeeee e eeee ee eeeeee eee, eeeeeee eeee Me8M, eee eeeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeeee eee eeeee eeeeeee ee e eeeeeeeee eeeeee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee ee eeeeee eee eeeeeeeeeeee eeee α-eeeeeeeee eeeeee.

Meeeeeee ‌88‌: Mee eeeeeee eeeeeeeee eee eeeeeeee eeeee eee MMM eeee ee (8M,8M)-8-eeeeee-8-eeeeee-8-[8-(eeeeeeeeeeeeeee)eeeee-8-ee]eeeeeeeeeeee-8-eee (‌88‌•MMM; 88 ee, 8.88 eeee, 8.88 eeeee) ee eee eeeeeeee ee M8M (8.88 eM, 8.8 eeee, 88 eeeee) eee MeMMM8 (88.8 ee, 8.88 eeee, 8.8 eeeee).

Meeeeeee ‌88‌: Mee eeeeeee eeeeeeeee eee eeeeeeee eeeee (8M,8M)-8-(eeeeeeeeee-8-ee)-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (‌88‌; 88 ee, 8.88 eeee, 8.88 eeeee) eee Me8MMM8M (88 ee, 8.88 eeee, 8.88 eeeee) ee eee eeeeeeee ee M8M (8.88 eM, 88 eeee, 88 eeeee) eeeeeee eee eeeeeeee ee MeMMM8.

Meeeeeee ‌88‌: Mee eeeeeee eeeeeeeee eee eeeeeeee eeeee (8M,8M)-8-(eeeeeeeeeeeee-8-ee)-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (‌88‌; 88 ee, 8.88 eeee, 8.88 eeeee) eee eeeee MMe (8.8 µM, 8.88 eeee, 8.88 eeeee) ee eee eeeeeeee ee M8M (8.88 eM, 88 eeee, 88 eeeee) eee MeMMM8 (88.8 ee, 8.88 eeee, 8.88 eeeee).

(M)-8-(8-Mee-8-eeeeeeeeeee)eeeeeeeeeeeee (‌88‌):[‌88‌]

Me e 8-eeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeee Me8MMM8M (88.8 ee, 8.88 eeee, 8.8 eeeee), (8M,8M)-8-(eeeeeeeeeeeee-8-ee)-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (‌88‌; 88.8 ee; 8.88 eeee, 8.8 eeeee), MMM (888 ee, 8.888 eeee, 8.88 eeeee), eee eeee-eeeeeeeeeeeee(8-eeeeeeeeeeeeee)eeeeee (888 ee, 8.88 eeee, 8.8 eeeee). Mee eeeeee eee eeeeee eeee e eeeeee, eeeeee ee −88 °M, eeeeeeeee ee eeee eeeeee (8.8 Meee), eee eeee eeeeeeeeee eeee eeeee. MMM (8 eM) eee eeeee ee eee eeeeeeee eeeeee eeeeeeee ee M8M (888 µM, 8.88 eeee, 88 eeeee) eee 8,8-ee-eeee-eeeeeeeeeeeee (888 µM, 8.8 eeee). Mee eeeeeee eee eeeeeeee eeee eeeeeeeeeee ee eeeeeee eeeeeeee eee eeeee eeeeeeeeeee (8 × 8 eee eeee) ee −88 °M eeee eeeeeeee eeeeeeee. Meeeeeeeeeeee (888 µM, 8.8 eeee, 8.8 eeeee) eee eeee eeeee ee eeeeeee, eee e eeeeeee ee eeeee eeeeeeee eee eeeeeeee eeeee eeee. Mee eeeeeeee eeeeee eee eeeee eeee eee −88 °M eeee eeee e −88 °M eeee eee eeeeeee eeee e eeee eeee ee eeeeee eee 88 e. Mee eeeeee eee eeeeeee eee Me8M (88 eM) eee eeeee ee eee eeeee eeeeeee, eeeee eee eeeeeee ee −88 °M eee 88 eee ee eeeeeeeeeee eee eeeeeeeee Me(MMM) eeeee. Meeeeeeeee eeeeeee eeeeee eee, eeeeeee eeee Me8M, eee eeeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeee e eeeeeeeee eeeeee, eeeee, eeee eeeee eeeeeeeeeeeeee (Meeeeeeeee eeeeee eee, Me8M/eeeeeeeee eeeee 8:88 ee 88:88, eeee eeeeeeee), eeeeeeee eee eeeee eeeeeeee ee e eeeee eeee eeeee; eeeee: 88.8 ee (88%); 88% ee. Meeeeeeeeeeee eee eeeeeeeeee ee eeeeeeeeeeeee eeeee eeeeeeeeeeeeee (MMM) eeeeeeee (Meeeeeeee MMM, 8–88% eMeMM/MM8, 888 ee eeeeeeee).

(M)-8-(8-Meeeeeeeeee)eeeeeeeeeeeee (‌88‌):[‌88‌]

Me e 8-eeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeee Me8MMM8M (8.8 ee; 8.88 eeee), (8M,8M)-8-(eeeeeeeeeeeee-8-ee)-8-eeeeee-8-eeeeeeeeeeeeeeeeee-8-eee (‌88‌; 88.8 ee; 8.88 eeee, 8.8 eeeee), MMM (888 ee, 8.888 eeee, 8.88 eeeee), eee MeMMM8 (88 ee, 8.8 eeee, 8.8 eeeee). Mee eeeeee eee eeeeee eeee e eeeeee, eeeeee ee −88 °M, eeeeeeeee ee eeee eeeeee (8.8 Meee), eee eeee eeeeeeeeee eeee eeeee. MMM (8 eM) eee eeeee ee eee eeeeeeee eeeeee eeeeeeee ee M8M (88.8 µM, 8.88 eeee, 88 eeeee) eee eeeeeeeeeeeee (88 µM, 8.8 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeeee eeee eeeeeeeeeee ee eeeeeee eeeeeeee eee eeeee eeeeeeeeeee (8 × 8 eee eeee) ee −88 °M eeee eeeeeeee eeeeeeee. Meeeeee (88 µM, 8.88 eeee, 8.8 eeeee) eee eeee eeeee ee eeeeeee, eee e eeeeeee ee eeeee eeeeeeee eee eeeeeeee eeeee eeee. Mee eeeeeeee eeeeee eee eeeee eeee eee −88 °M eeee eeee e −88 °M eeee eee eeeeeee eeee e eeee eeee ee eeeeee eee 88 e. Mee eeeeee eee eeeeeee eee Me8M (8 eM) eee eeeee ee eee eeeee eeeeeee, eeeee eee eeeeeee ee −88 °M eee 88 eee ee eeeeeeeeeee eee eeeeeeeee Me(MMM) eeeee. Meeeeeeeee eeeeeee e Meeeeeee eee eeee Me8M eeee eeeeeeee ee eeeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeee e eeeeeeeee eeeeee, eeeee, eeee eeeee eeeeeeeeeeeeee (Meeeeee, Me8M/eeeeeeeee eeeee 8:88 ee 88:88, eeee eeeeeeee), eeeeeeee eee eeeeeee eeeee ee e eeeeeee ee eeeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee MMM (8 eM) eee eeeeeee eeee Me/M (8 ee). Mee eeeeeee eee eeeeeeee, eeeeeee eeee M8, eee eeeeeee eeeee M8 (eeeeeee) ee eeeeeee eeeeeeeeeee eee 8 e. Mee eeeeeee eee eeeeeeee eeeeeee Meeeee eee eeeeeeeeeeee. Meeeeeeeeeee ee eeeeee eee (Me8M/eeeeeeeee eeeee 8.8:88.8 ee 88:88) eeeeeeee eee eeeee eeeeeeee; eeeee: 88.8 ee (88% eeee eee eeeee); 88% ee. Meeeeeeeeeeee eee eeeeeeeeee ee MMMM eeeeeeee (Meeeeeeee MMM, eMeMM/eeeeeee 8:88, 888 ee eeeeeeee).

References