Science of Synthesis

Benohoud, M.; Hayashi, Y., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 126.

Less common imines such as N-alkylimines, cyclic imines, and imines derived from ketones (ketimines) have also been investigated as acceptors in the organocatalyst-mediated Mannich reaction of carbonyl compounds. The enantioselective Mannich reaction of ketimines is very limited, although the substrates would constitute an interesting template for the synthesis of quaternary β-amino carbonyl compounds.

Mee α-eeeeeeeeeeeeeeee ee eeeeeeeee eee ee eeeeeeeeeeeeee-eeeeeeee Meeeeee eeeeeeee eee eeee eeeeeeeeee. Meeeeee, ee eee eeee ee eee eeeee-eeeeeeeee eeeeeeee eeeeeeeee ee eeeeeeee, eeeeeeeeeeee, eee 8-eeeeeeeeeeeeee, eee eeeeeee eeeeeee eee eee eeeeeeee. Meeeee eeeeeee eeee eeeeeeeeeeee eee eee eeeeee eeeeee eee eeeeeeee eeee eeeeeeeee.[‌88‌] Mee eee ee (eeeeeeeeeeeee)eeeeee eeeeee eeeee ‌888‌, ee eeeeeee eee eeeeeeeeee, eeeee eeeeeeee eee α-eeeeeeeeeeeeeeee ee eeeeeeeee.[‌88‌,‌88‌] Meeeeeeeeeeeeeee eeeee eeeee ‌88‌ eeeee eee eeeeeee eeeeeeeeeeeeeeeeee eee eee eeeeeeee eeee eeeeeeeee. Mee eeeeeeeeee eee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeee ee eee eeeeeeee ee 88 eee% ee eeeeee eeee. Mee eeeeeeee ee eeeeeee eeeeeee[‌88‌] (8 eeeee) eeee eeeeeeeee eee eeee ee eee eeeeeeee eeeeeeee eeee 8 M eeeeeee eeeeeeee.[‌88‌] Meeeeee eeeeeeeee eeee eeee eeee, eeeeeee eee eeeeeeeeee ee eee eeeeeee, eee eee eeeeeeeee eeeeeee ‌888‌ ee eee Meeeeee eeeeee ee eeeeeeee ee eeee eeeeee (88–88%) eeee eeee eeeeeeeeeeeeeeeeeeee (88–88% ee) (‌Meeeee 88‌).

‌Meeeee 88‌ α-Meeeeeeeeeeeeeee ee Meeeeeeee Meeeeeeee ee e Meeeeeeeeeeeeeee Meeee Meeee[‌88‌,‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee MMMM eeeeeeee ee ‌888‌.

Meeeeee eee eeeeeeeeeee eeeeeeeeeee eeee eeee eeeeee ee eeeeeeeee eee eee eeeeeeee eee eeeeeeeee ee eee eeeeeee Meeeeee eeeeee eeee eeee eeeeeeeeee. Meeeeee, eee eeeeeeeeeeee eeeeeeeeee eeeeeeee eeee (M)-eeeeeee (‌8‌) ee 8-[(8M)-eeeeeeeeee-8-ee]-8M-eeeeeeeee (‌88‌) ee eeeeeeee ee eeee eeeeeeee eeee eeeeeeee eeeeeeeeeee eeee ee ‌88‌ ee eee eeeeeeee. Me eeeeeee eeee eeeeeeee, ee eeeeeeeeeeeee eeeeeeeeee ee eeeeeee ee eeeeeeeeeee ee eee eeeeeee-eeeeeee eeeeeee eee e eeeeee eeeeeeeee ee eee eeee ee eeeeeeeeeee eeeeeeeeeee ee eeeeeeee (‌Meeeee 88‌).

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

Meeeee eeeeeee eeee eeeeeee eee eeee eeeeeeee eeee eeeee eeeeeee eeee eeeeeeeee eeeeee eeeeeeeeeeee eeeeeeeee, eee ee eeeeee eeeeeeeee eee eeeeeeeeee eeeeeee. M eeeeee ee eeeeeeeee eee eeee eeeeeeee ee eeeee eee eeeeeeeeee eeeee ee eee eeeeeeee eeee ee eeeee ee ee α-eeee eeeeeeeeeee ee eee eeeee.[‌888‌] Mee eeeeee eeeeeee 8-[(8M)-eeeeeeeeee-8-eeeeeeee]eeeeeeeeeee (‌888‌; 8 eee%) eeeeeeeee eee Meeeeee eeeeeeee ee eeeeeeeee ‌888‌ eee eeeeeeeee. Mee Meeeeee eeeeeee ‌888‌ eee eeeeeeee ee eeee eeee eeeeee (88–88%), eeee eeeeeeee ee eeee eeeeeeeee- eee eeeeeeeeeeeeeeeeeeee (ee 8:8 ee >88:8 eee 88–88% ee) (‌Meeeee 88‌). Meeeeeee eeeeeee eeeeeee eee eeeeeee eeeeeeeeeeee eee eee eeeeeeee eeee ee eee eeeeeeee eeeeee eeeee ee eeee eeee. Mee eeeeeee eeeeeee e eeeeeeeeee-eeeee eeeee ee eeeee eee Me eeee ee eee eeeeeee eeeeeee eee Me eeee ee eee eeeeeeee ee ee eeeeeeeeeeeeee eeeeeeee ee eeeeeeee eee eeeeee eeeeeeeeee ee eee M—M eeee-eeeeeee eeee (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeee Meeeeeee ee Meeeeeeee eeee Meeeeeeee Meeeeeeee ee e Meeeee Meeeeee[‌888‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee MMM eeeeeeeeeeee ee eee eeeee eeeeeee.

e Meeeeeeeee ee MMMM eeeeeeee.

e Meeee ee eeeeeeee eeeeeee.

e MM8Me8 eeee ee eeeeeee.

‌Meeeee 88‌ Meeeeeee Meeeeeeeee Meeee Me Meeeeee eee Meeeeeee Meeeeeeeeeeeeeeee[‌888‌]

Mee Meeeeee eeeeeeee ee 8-(eeeeeeeeeeeeeee)eeeeeeeeee-8(8M)-eeee ‌888‌ eee eeeeeee eee eeee eeeeeeeeeeee[‌888‌] eee eee eeeeee eeeeeee 8-[(8M)-eeeeeeeeee-8-eeeeeeee]eeeeeeeeeee (‌888‌), ee eeeeeeeeeee eeee eee Meøeeeee eeee eeeeeeeee-e-eeeeeeee eeee, eeeee eee eeee eeeeeee ee eeeee ee eeeeee eee eeeeeeeeeee. Mee eeeeeeeee ee eeeeeeee eeee eeeee ee eeee ee eeeeeeeee ee eee eeeeeeeeeeeeeeeee ee eee eeeeeeee. Mee eee ee 88 eee% ee eeeeeeee eee 88 eee% ee eee eeeeee eeeeeeee eeeeee eee eeeeeeeee ee eeeeeee Meeeeee eeeeeee ‌888‌. Meeeeee, eee eeeeeeeee ee eee eeeeeee ee ee eeeeeeeee eeeeeeeeee eee eee eeeee eeeeeeeee eeeeeeeeeeee. Mee eeee eeeeeee eee eeeeeeee ee eee eeee ee eeeeee eeeee ee eeeeeeeeeee eeeeee eeeeeee (88–88%) eeee eeeeeeee eeeeeeeeeeeeeeeeeeee (88–88% ee) (‌Meeeee 88‌). Mee eeeeeeeeeeeee ee eee Meeeeee eeeeeee eee ee eeeeee eeeeeeeee ee >88% eeeeeeeeeeee eeeeee ee e eeeeee eeeeeeeeeeeeeeeee ee eeeeeee.

‌Meeeee 88‌ Meeeeee Meeeeeee ee 8-(Meeeeeeeeeeeeee)eeeeeeeeee-8(8M)-eeee eeee Meeeeee Meeeee Meeeeee[‌888‌]

Meeeeeeee, eeeeeee eeeeeeeee eee eeeeeeee ee eeeeeeeeeeeee ee Meeeeee eeeeeeeee. Me eeeeeeeeee Meeeeee eeeeeeee ee eeeeee eeeee ‌888‌ eee eeeeeee eeeeeeeee ee (M)-eeeeeee (‌8‌) eee eeee eeeeeeeee. Mee eee ee 88 eee% ee eeeeeeee eeeeeee eee eeee-Meeeeee eeeeeee ‌888‌ ee eeeeeeee ee eeee eeeeee (88–88%) eee eeee eeee ee eeeeeeeee eeeeeeeeeeeeeeeeeee (ee 88:8 ee >88:8 eee 88 ee >88% ee).[‌888‌] Meee eeeeeee, eeeee eeeeeeeeeeeeeeeeee ee eeeeeeee (88% ee). Me eee eeee ee eeeeeeeeeeeee eeeeeee, eeeee eeeeeee ee eeeeeeeeeeee eee eeeeee (‌Meeeee 88‌).

‌Meeeee 88‌ eeee-Meeeeee Meeeeeee ee Meeeeee Meeeeee eee Meeeee Meeeee Meeeeeeee ee (M)-Meeeeee[‌888‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee MMM eeeeeeeeeeee ee eee eeeee eeeeeee.

e Meeeeeeeee ee MMMM eeeeeeee.

e Meeee ee eeeeeeee eeeeeee.

e M eeeeeee ee eeeeeeeeeeee eee eeeeeeee.

Meeee eeeeee eeeeee eeee eeee eeeeeeee ee Meeeeee eeeeeeeee, eee eeeeeeeee ‌888‌ (M = M) eee eeeeeeee ‌888‌ (M = M) eee eeeeeeeee eeeeeeeeeeeee eee Meeeeee eeeeeeeee ee eeeeeee.[‌888‌] (M)-Meeeeee (‌8‌) ee eee eeee eeeeeeeee eeeeeeee eeeee eeeeeee eeeee eeeeee eeeee eeeee eeeeee. Mee eeeeee eeeeeeee eeeeee eeeeeeeeeee ee eee eeeeeeeee eeeee. Meeeeeeee eeeeeeeee eeeeeeeeeeeee ee eeeee ee eee eeeeeee, eee eee eee eeeeeeeeeeee ee eee eeeeeeee ee eeeeeee eeeeee eeeeeeee eee eeeeeeee ee e eeeee eeeeeeeee eee eeee ee e eeeeee. Meeeeeeeee eee eeee ee eee eeeeee eeeeeeeeeee ee eee eeeeee eeeee ee eeeeeeeee eeeeee (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeee Meeeeeee ee Meeeeee eee Meeeeeeeeeeeeee Meeeeeeee ee (M)-Meeeeee[‌888‌]

Meee eeeeee eeeeee eeee ee β-eeeeeeeee eeeeeeeeeee eeeee eeee eeeeeee ee eee eeeeeeee ee (M)-eeeeeee (‌8‌).[‌888‌] 8-Meeee-8,8-eeeeeee-β-eeeeeeeee (‌888‌) eeeeee eeee eeeeeeeee eeeeeee (eeee ee eeeeee) ee eeee eeeeee ee M8-eeeeeeeeeee 8,8,8,8-eeeeeeeeee-β-eeeeeeeee eeeeeeeeeee ‌888‌ eeee eeeeeeee ee eeee eeeeee (88–88%) eee eeee eeeeeeeeeeeeeeeeeeee (88–88% ee) (‌Meeeee 88‌). Mee eeeeeeee eeeeeeee ee eee eeeeeeee ee 8–8 eee% ee eeeeeeee ee eee eeeeeeee eeeeeeeee; eeeeeee, eee eeeeeeee eeeee eee eeeeeeeee eeee (eeeeeee eeee).

‌Meeeee 88‌ Meeeeee Meeeeeee ee β-Meeeeeeee Meeeeeeeeee eee Meeeeee Meeeeeeee ee (M)-Meeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-(Meeeeeeeeeeee) Meeeeeee ‌888‌; Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eeeeeeee ‌88‌ (8.88 e, 8 eeee) ee e 8 M eeee ee MeMe ee MMM (8 eM) ee −88 °M eee eeeee e eeee ee MeMM (88 µM, 8 eeee) ee e 8 M eeee ee MeMe ee MMM (8 eM). Mee eeeeeeee (88 eeee) eee eeeee, eee eee eeeeeee eee eeeeeee eee e eee eee, eeeeeeee ee eee eeeeeeee ee (eeeeeeeeeeeee)eeeeee eeeeee eeeee (‌888‌; 8.88 eM, 8 eeee). Mee eeeeeee eee eeeeeee ee −88 °M eee 8 e. Mee eeeeeeee eee eeeeeee ee eeee ee eeeeeeee ee MeMM8 (8.88 e, 88 eeee) eee MeMM (88 eM). Mee eeeeeee eee eeeeeee eee e eee eee ee −88 °M eee ee 8 °M eee eeeeeee 88 eee. Mee eeeeeee eee eeeeeeee eeee eee. MM8Me (88 eM) ee 8 °M eee eeeeeeeee eeee Me8M (8 × 888 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M (88 eM) eee eeeee (88 eM) eee eeeee (MeMM8), eee eee eeeeeee eee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88); eeeee: 88–88%; 88–88% ee.

8,8-Meeeeeeeeeeeeeeee-8-eeee ‌888‌; Meeeeee Meeeeeeee:[‌888‌]

Me e eeee ee 8,8-eeeeeeee-8,8-eeeeeee-8M-8,8-eeeeee-8-eee (‌888‌; 8 eeeee) ee eeeee MMMM (8.8 M) eee eeeee (M)-eeeeeee (‌8‌; 8.8 eeeee) eee eee eeeeee (8 eeeee). Mee eeeeeee eee eeeeeee eee 88 e eee eeeeee eeee e eeeeeeeeee eeeeee eeeeeeeeee eeeeeee/MeMMe (8:8) eee eeee-eeeee MM8Me eeee. Mee eeeeeee eeeeeeee eee eeeeeeeee eeee eeeeeee/MeMMe (8:8; 8 ×). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee MMMM (eeeeeeee eeeeeee/Me8M) eeeeeeeee eee eeeeeee ee e eeeee eeeeeeeeeee eeeee. Meeeeeeeeee eeeeeeeeee eeeeeeeeeeee eee eeee eeeeeeee eee eeeeeeeeeeeeeeeee (MM8Me8/eeeeee) ee eee eeeee eeeeeeee ee eeeeeeeeeeeee ee e eeeeee eeeeeeeeee eeeee eeeeeeeeeeeeeee eeeeee; eeeee: 88–88%; 88 ee >88% ee.

References