Science of Synthesis

Liu, L.; Wang, D.; Li, C. -J., Science of Synthesis: Stereoselective Synthesis, (2011) 2, 615.

It should be noted that if this copper(II)-mediated vinylogous aldol reaction is performed on a preparative scale (35.5 mmol), because of its exothermic nature, the slow addition of (benzyloxy)acetaldehyde (‌48‌) to a sufficiently cooled (−90 °C) solution of the 2,6-bis[(4S)-4-phenyl-4,5-dihydrooxazol-2-yl]pyridine (Ph-pybox) derived copper(II) catalyst ‌47‌ and the disilyl dienol ether ‌50‌ is required to afford the condensation product. Subsequent reduction gives the anti-diol ‌105‌ (‌Scheme 44‌).[‌52‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeee ee e Meeeee Meeeee(MM)/Me-eeeee Meeeeee[‌88‌]

M8-Meeeeeeee eeeee eeeeeeeeeee eeeeeee[‌88‌,‌88‌] eeee eeee eeee eeee ee eee eeeeeeeeee eeeeeeeeee Meeeeeeee eeeee eeeeeeee ee 8-(eeeeeeeeeeeeeee)eeeee (‌888‌) eee eeeeee eeeeeeee. Meeee eee eeeeeeeee ee eeeeee(MM) eeeeeeeeeeeeeeeeeeeeeeeee eee eeeeee eeeeeeeeeee ‌888‌, eee eeeee eeeeee ‌888‌ ee eeeeeeee eeee eeee eeeeeeeee- eee eeeeeeeeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeee ee e Meeeee Meeeee(MM)/Meeeeeeeeee Meeeeee[‌88‌]

Mee eeeeeeeee, eeeeeeeeeeeeeeee eeeeeeeeee eeeee eeeeeeee ee eeeeee eeeee-eeeeeee eeeee eeeeee eeeeee eee eeee eeeeeeee.[‌88‌] Me eee eeeeeeee ee eee (M)-8,8′-eee(ee-8-eeeeeeeeeeeeee)-8,8′-ee-8-eeeeeeee [(M)-MeeMMMMM] (‌88‌)/eeeeee(MM) eeeeeeee eeeeeeee eee eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee (MMMM), eee eeeeeeee ee eee eeeee eeee-8-eeeeee eeeeeee eeeee eeeeee eeeee ‌888‌ ee eeeeeee eeeeeeeee eeeeeeee eeeeeeee ee eeeeeeee (e.e., ‌888‌) eeee eeeeeeeee eeee eeeeeeeeeee (>88:8) eeeee eeee eeee eeeeeeeeeeeeeeeeee eee eee eeeeee eeeeeeeeee eeeee eeeeeeee (‌Meeeee 88‌). Meeeeeee, eee eeeeeeeee eeeeee eee ee eeeeeeee ee eee eeeeeeeeee eeeeeeeeee Meeeeeeee eeeee eeeeeeeee ee eeeeeeeee eeeeeee.

‌Meeeee 88‌ Meeeeeeeee Meeeeeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeee ee e Meeeee Meeeee(MM)/MeeMMMMM Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8M)-Meeeee 8-(Meeeeeeee)-8,8-eeeeeeeeeeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeee eeee ee [Me(Me-eeeee)](MeM8)8 (‌88‌; 8.8 eM, 8.88 eeee, 8.88 eee%) eee eeeee eeee 88 eee ee e eeee ee MeMMM8MMM (‌88‌; 8.8 e, 8.8 eeee) ee −88 °M eeeeeeee ee eeeeeeee ee e eeee ee eee eeeeee eeeeeeeeeeee eeeeeee eeeee eeeeee eeeeee ‌88‌ (8.8 e, 8.8 eeee) ee MM8Me8 (8 eM). Meeee 8 e ee −88 °M, MMM eeeeeeeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee. Mee eeeeeee eee eeee eeeeeeee eeeeeee e 8.8 × 8 ee eeee (eeeeee eee) eeee Me8M (888 eM). Meeeeeeeeeeee ee eee Me8M eeee eeee e eeeee eee, eeeee eee eeeeeeeee ee MMM (888 eM) eee 8 M ee MMe (88 eM). Meeee eeeeeeee ee ee eee 88 eee, eeee eeee eee eeeeee eeee e eeeeeeeeee eeeeee eee eeeeeee eeee Me8M (888 eM). Mee eeeeeee eeeee eee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeee eeee eee. ee MeMMM8 (88 eM) eee eeeee (88 eM), eee eeeee (MeMM8). Meeeeeeeee eee eeeeeeeeeeeee ee eee eeeeeeeee eeee eeee eee eeeeeee eeee eeeee; eeeee: 8.8 e (88%).

Mee eeeeeee eeee eeeee eee eeeeeeeeeeee eeeeeee ee eee eeee-eeee ee eeeeeee: M eeee ee Me8MMM(MMe)8 (88.8 e) ee MeMM (88 eM) eee eeeee eeee 88 eee ee e eeee ee eee eeee eeeee ee MeMM (888 eM) ee −88 °M. Mee eeeeeeeee eeeee eeeee eeee eee eeeeeee ee −88 °M eee 88 e eee eeee eeeeeeee ee eee eeeeeeee ee eee. Me8MM8. Mee eeeeeee eeeee eee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeee eeee eeeee (88 eM), eeeee (MeMM8), eee eeeeeeeeeeee ee eeee eee eeee-eeee ‌888‌ ee e eeeee eeeee; eeeee: 8.8 e (88%); 88% ee (eeee); ee (eeee/eee) 88:8 [MMMM eeeeeeee, Meeeeeeee MM-M eeeeee, eeeeee/eMeMM 88:88, 8.8 eM · eee−8; eM(eeeee) 88.8 eee; eM(eeeee) 88.8 eee]; [α]M +8.8 (e 8.8, MMMe8).

Meeeee (8M)-8-Meeeeee-8-[(8M)-8-eee-8,8-eeeeeeeeeeee-8-ee]eeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌88‌]

M eee Meeeeee eeee eeeee eeeee eee eeeeeee eeee Me(MMe)8 (8.88 eeee) eee (M)-eeeee eeeeeeeeeee ‌888‌ (8.88 eeee). Meeee Me8M (8.8 eM, 8.8 M) eee eeeee eee eee eeeee eeee eee eeeeeee ee ee eee 88 eee. Meeeeeeeeeee, M8MMM8MM (8.88 eeee, 8.8 eeeee), eeeeee eeeeeeee (8.8 eeee), eee 8-(eeeeeeeeeeeeeee)eeeee (‌888‌; 8.88 eeee, 8.8 eeeee) eeee eeeee, eee eee Meeeeee eeee eee eeeeee. Meeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee (8–8 e, MMM eeeeeee), eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee 8M MMM eeeeeeeeeeee ee eeeeeeeee eee ee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee/MeMMe 8:8) ee eeee eee eeeeeee ee e eeeee eeeeee eee; eeeee: 88%; 88% ee; 88% ee [MMMM eeeeeeee, Meeeeeeee MM-M eeeeee, eeeeee/eMeMM 8:8, 8.8 eM · eee−8, 888 ee, 88 °M; eM(eeeee) 88.8 eee; eM(eeeee) 88.8 eee]; [α]M 88.8 (e 8.8, MMMe8).

(+)-(8M,8M)-8-(8,8-Meeeeeeeeeeeeee)-8-eeeeee-8,8-eeeeeeeeeeee-8-eee (‌888‌); Meeeeee Meeeeeeee:[‌88‌]

Meeee eeeee, e eeeeeee ee Me(MMe)8 (8.8 ee, 8.88 eeee, 88 eee%) eee (M)-MeeMMMMM (‌88‌; 88.8 ee, 8.888 eeee, 88 eee%; eeeee ee 888 °M eeee M8M8 eeeee ee eee) ee MMM (8 eM; eeeeeee eeeeeeeee eeee Me/eeeeeeeeeeee) eee eeeeeee eeee 88 eee. M eeeee eeeeee eeee eee eeeeeeee. M eeee ee eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeee (MMMM; 88.8 ee, 8.8 eeee, 88 eee%) ee MMM (8 eM) eee eeeee eeeeeeee eee, eeeee 88 eee, e eeeeee eeeeee eeee eee eeeeeeee. 8-Meeeee-8-(eeeeeeeeeeeeeee)-eeeee-8,8-eeeee (‌888‌; 888.8 ee, 8.88 eeee) eee eeeee eeeeeeee eee eee eeeeeeeee eeee eeeeee ee e eee-eeeee eeeee. Meee, 8,8-(MeM)8M8M8MMM (8.8 eeee) eee eeeeee eeeee eee eee eeeeeee eee eeeeeee eee 88 e ee ee. Mee eeeeeee eee eeeeeee eeee eee. ee MM8Me eee eeeeeeeee eeee MeMMe. Mee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8), eee eeeeeee eeeeeee eee eeeeeeee ee e eeee eeeeee eeeeee; eeeee: 88%; 88% ee [MMMM eeeeeeee, Meeeeeeee MM eeeeee, eeeeee/eMeMM 88:8; eM(eeeee) 88.8 eee; eM(eeeee) 88.8 eee]; [α]M88 +8.8 (e 8.88, MMMe8).

References