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36.1.2.1.7.7 Variation 7: Using Meerwein–Ponndorf–Verley-Type Reactions

DOI: 10.1055/sos-SD-036-00032

Cox, L. R.Science of Synthesis, (200836102.

MeerweinPonndorfVerley reductions are reversible processes; thus, in order to drive the equilibrium over to the desired alkanol product, reactions are traditionally carried out at elevated temperatures. When aluminum triisopropoxide is employed as the reducing agent, propan-2-ol is used as the solvent and the volatile acetone byproduct is removed from the reaction by distillation as it is generated (Scheme 46).[‌445‌‌448‌]

Meeeee 88 MeeeeeeeMeeeeeeeMeeeee Meeeeeeee ee Meeeeeee Meeeeeeee ee e Meeeeeeeee Meeeeee

Mee eeeeeeeee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee eeeeeee eeee e eeeee ee eeeeeeee. Mee eeeeeeee eeeeeeee eeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeee (eeeee ee eeeeee), eee ee ee eeeeeeeeee eeeeeeeee ee eeeee eee eeeeeeee ee eeeeeeeeee. Meee eeeeeeeee eeeeeeeeeeee eee eee eeeeee eeeeeeeeee eeee eeeeeee eeeeeeeeee, eee e eeeeee ee eeee eeeeeeeee, eeeee eee Meeeeeeeee eeeeeeeee ee eeeeeeeeee, eee eeeeeeee eee eeeee ee eee eeeeeee eeeeeee eeeeeee. Meeeeeeeeee, e eeeeee ee eeeeeeee eeee eeeeeeeeeeeee eeeeeeee eee eeeeeeeee eeeeeee ee eeee eeeeeeee. Meeeeeeee eeeeeeeeeee eee eeee eeeee ee eeeeeee eeee eee eeee ee eeeeeeee eee eee eeeee ee eee eeeeeee eeeeeee.[‌888‌] Mee eee ee eeeeeeeeeeeeee eeeeeeeeee ee eeeeeeeeeeeeeee eeee eee e eeeeeee eeeeee, eeeeeeee eee eeeee eeeeeeeee ee eeeeeeeee (eee eeeeeee) ee eeeeeeee 88 ee eeee eeeeeeeeeee (Meeee 88, eeeeeee 8, 8);[‌888‌] eeeeee, eee eeee eeeeeeee eeeeeeeee (eee eeeeee eeeeeee), eeee eee eeee eeeeeeee eee eeeeeeee eeeeeeee eee ee eeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeeee (eeeeeee 8, 8).[‌888‌] Mee eeeeee eeeeeeee eeeee eee eeeee eeee-eeeeeeee MeeeeeeeMeeeeeeeMeeeee eeeeeeeeee eee eeee ee eeeeeeeeeeee(eeeeeeeeeeeeeeee)eeeeeeee, ee eeee eeeeeee eeee eeeeeee eeeeeeeee (eee eeeeeee) ee eeee eeeeeeeeeee (eeeeeee 8, 8).[‌888‌]

Meeee 88 MeeeeeeeMeeeeeeeMeeeee-Meee Meeeeeeee ee Meeeeeeee[‌888‌‌888‌]

Meeee M8 Meeeeeeeee Meeee (%) Mee
8 (MM8)8Me Me(MeMe)8 (8 eeeee), MMM (8 eeeee), eeeeeee, ee, 88eee 88 [‌888‌]
8 Me Me(MeMe)8 (8 eeeee), MMM (8 eeeee), eeeeeee, ee, 88eee eeeee [‌888‌]
8 Me Me(MeMe)8 (8eee%), MMM (8eee%), eMeMM (8 eeeee), eeeeeee, ee, 88eee 88 [‌888‌]
8 8-M8MM8M8 Me(MeMe)8 (8eee%), MMM (8eee%), eMeMM (8 eeeee), eeeeeee, ee, 88eee eeeee [‌888‌]
8 Me Me(MeMe)8(MMMMM8) (8 eeeee), MM8Me8, ee, 88eee eeeee [‌888‌]
8 (MM8)8Me Me(MeMe)8(MMMMM8) (8 eeeee), MM8Me8, ee, 88eee 88 [‌888‌]
8 Me MeMe8 (88eee%), eMeMM (8 eeeee), eeeeeee, ee, 8e 88 [‌888‌]
8 Me MeMe8Me (88eee%), eMeMM (8 eeeee), eeeeeee, ee, 8e 88 [‌888‌]
8 Me Me(MeMe)8eMeMM (8 eeeee), (±)-MMMMMe (8.8 eeeee), eeeeeee, ee, 8e eeeee [‌888‌]
88 Me Me(MeMe)8eMeMM (88eee%), (±)-MMMMMe (88eee%), eMeMM (88 eeeee), eeeeeee, ee, 8e eeeee [‌888‌]
88 8-M8MM8M8 e-MeMMeM8 (88eee%), eMeMM (8 eeeee), MMM, 88°M, 88e 88 [‌888‌]
88 (MM8)8Me e-MeMMeM8 (88eee%), eMeMM (8 eeeee), MMM, 88°M, 88e 88 [‌888‌]
88 Me Me{M[MM8(MM8)8MM8]8}8 (88eee%), eMeMM, 88°M, 8e 88 [‌888‌]
88 Me Me (8 eeeee), M8 (8eee%), eMeMM, 88°M, 88e 88 [‌888‌]
88 Me Me (8 eeeee), M8 (8eee%), eMeMM, 88°M, 88e 88 [‌888‌]

e MMMMM=8,8-eeeeeeeeeeeee-8,8-eeee.

M eee eeeeeee eee eee MeeeeeeeMeeeeeeeMeeeee eeeeeeee eeeeeeee eee eeeeeeeeeeee ee e eeeee ee eeeeee eeeeee eeeeeeee eeeeeeee eeeeeeeee, eeeee eee ee eeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeeee.[‌888‌‌888‌] Mee eee ee-eeeeeee eeeeeeeeee eee eeeeeeee eeeeeeee 88, eeeee eee ee eeeeeeeee ee eeee eeee eeeeeeeeeeeeeeeee, eeeeee-8-ee, eee eee eee-eeeeee 88, eee eeeeeeee eeeeeeeee eeeeeeee, e.e. ee eeee 88 (Meeeee 88).[‌888‌,‌888‌] Meee eeeeeee eeeeeeee eeeeeeeee eeee eeee eeeee ee eeeeee eeeeeeeee. Mee eeeeeee, eeeeeeeee eeeeeeeee ee eeee eeee eeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeee eeeeeeee eee eeeeee-8-ee ee ee eeeeee eeeeeee eeee eeeeee eee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee ee eeeeeeeee (eee eeeeeee) (Meeee 88, eeeeeee 8, 8).[‌888‌]

Meeeee 88 Me Meeeee Meeeeeee Meeeeeee Meee Meeeeeeeeeeee Meeeeeee eee Meeeeeeee Meeeeee ee eee MeeeeeeeMeeeeeeeMeeeee Meeeeeee[‌888‌,‌888‌]

Meeee eeeee eeeeeeeee, ee eeeeeeeeee eeeeeeeee eeeeeeeee,[‌888‌,‌888‌‌888‌] eeee eeeeeeee eee eeeeeeeee ee eeeeeeeee (eee eeeeeee) eee e MeeeeeeeMeeeeeeeMeeeee-eeee eeeeeeee eeeeeeeee. Mee eeeeeee, e eeeeee eeeeeeee eeee eeeeeeeee(MM) eeeeeeeeeeee eee (±)-8,8-eeeeeeeeeeeee-8,8-eeee eeeeeee eeeeeeeee ee eeeeeeeee eeeee ee eeee eeeeeeeeeee (Meeee 88, eeeee 8).[‌888‌] Mee eeeeeeee eee ee eeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeee (eeeee 88). Meeee 8 eeeeeeeeeeee, ee eeeeeeeeee eee(eeeeeeeeeeeeeeee)eeeeeeeee(MM) eeeeeeeeeeeeee eee eee(eeeeeeeeeeeeeeee)eeeeeee(MM) eeeeeeeeee, eeee eeeeeeee eee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee ee eeeeeeeee ee eeeeeeee 88 ee eee eeeeeeee ee eeeeeee (Meeeee 88).[‌888‌] Meeeeeeee e eeeeeeeee eeeeeeee eeeeeeee ee e eeeeee eeeeeee eeeeeeee e eeeeeeeee eee eeeeeeeeeeee eee eeeeeeee eee eeeeeeeeeeee eeeeee.[‌888‌,‌888‌]

Meeeee 88 Meeee 8 Meeeeeeeeeee eee eee MeeeeeeeMeeeeeeeMeeeee Meeeeeeee ee ee Meeeeeee[‌888‌]

Meeeeeeeee eeeeeeeee eee eeeeeeeee eeeeeeeee eee eee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee ee eeeeeeeee (eee eeeeeee).[‌888‌‌888‌,‌888‌] Meeee eee ee-eeeeeee eeeeeeeeeeee eeee eeeeeeeeee eeee eeeeeeeee eee eeeeeeeeeeee eeeeeeeee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee, eeeeeeeee eeeee eee eeeeeeeeee eeeeeeee eeee eee eeeeeeee eeeeeee. Me eeeee eeeee eeeeeeeeeeee, eeee-eeeeeeeeeeeeee(MMM) eeeeeeee eee eee eeee eeeeeeeee eeeeeeee (Meeee 88, eeeeeee 88, 88).[‌888‌] Mee eeeeee Meeee eeeeee eeeeeeeee(MMM) eeee[(eeeeeeeeeeeeeeeeeeeeee)eeeeeee] ee eeee ee eeeeee eeeeeeee eee eee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee ee eeeeeeeeeeee eee ee eeee eeeeeeeee eeee eeeeee eeeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeee ee eeeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeeeee (eeeee 88).[‌888‌] Me eeee eeeeeeeee ee eeeeeeee(MMM) eeeeeeeeeeee eeee eeeeeeee eeeee eee eeeeee ee eeeeee-8-ee ee e eeeeeeeeeee eeee eeeeeeeeeeeeeee eeeeee eee eeeeeeee eeeeeeee eeeeeeeee ee eeee eee. Meeee eeeeee-8-ee ee eee eeeeeee eee eeeeeeee ee eee eeeee (eeeeee eeee eeeeee, eeeeeeeee, ee eeeeeeeee) ee eeeeeeeee eee eeeeeeeeee eee eeeeeeeee ee eeeeeee eeeeeeee. Meeeee ee eee eeeeeee eeeeeee eeeeeee eee eeeeeeeee eeee, eeeeeeee ee eeee eeeee eee eeeeeeeee ee eeeee eeeeeeee, eeeeeee eeee eee eeeeeee eeeeeeeee eeee eee eeeeeee eeeeeeeee eeeeeeee eeee eee eeeeeeee eeeeeeee, eeeee ee eeeeeeeeee eeeeee ee eee eeeeeee eeeeeee (eeeeeee 88, 88).[‌888‌]

Meeeeeeeeeeeee eeeeeeee eeeeeeeeee eeeee eeeeee eeeee eeeeeee e β-eeeeeee eeeeeeeeeee, ee eeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeee,[‌88‌,‌888‌] eeeeee eeeeeeeee (eee eeeeeee) ee eee eeeeeeeeeeeee eeeeeeee. Meeeeeeeeeeeeeeeeee eee eeee eeee eeee,[‌888‌] eee ee eeee eeeeeeee eeee eeeeeeeeeeeeeeeeee eeeeeee eee eeeeeeeee eee ee ee eeeeeeee ee 8 ° M eee eeeee. Meeee eeeeeeeeeeeeee eeeeeeee, eeee ee eeeeeeeeeeeeeeee, eeeee eeeeeeeee, eeeeeeee ee eeeee eeeee e eeeeeeeee eeeee eeeeeeee eeeeeeee eee ee e eeeeeee. Meeeeeeeeeeeeeeeee eeeeeee ee e eeeeeeeeeeee eeeeee eee eeeeee eeee eeeeeee; ee eeeeeeeee eee eeeeeeeeee eee ee eeeeeeeeee ee eeeeeeeee eee eeeeeee ee e Meeee eeeeMeeee eeee eeeeeee eeee eeeeeeee eeeeeee.[‌888‌] Meeeeee eeeeeeee eeeeeee eeeeeeeeeeeeeeeeee eeeeeeee,[‌888‌] eeeeee- eee eeeeeeeeeeeeeeeeeeeeeeeee,[‌888‌‌888‌] eee eeeeeeeeeeeeeeeeeeeeeee.[‌888‌] Me eeeee, eeeeeeeeeeeeeeeeee eeeeeeee ee ee eeeeeeeeee eeeeeeee: eee eeeeeeeeeeeeee eeeeeeeee ee eeeeeeeee ee eee eeeeeeee ee eeee eeeeeeeee eee eeeeeee, eeee eeeeeeeee eeeeee eeeeeee, ee eeeeeee eeeeeeee eeee eeee eeeeeee. Meee eeeeeeeeeeeee, ee eee eeee eeee eeee ee eeeeeee eeeeeeeee eeeeeeeeee eeeeeee eeeeeeeee eeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeeeeeee Meeeee Meeeeeeeeee Meeeeee ee Meeeeeeeeeeeeeeeee Meeeeeee ee Mee Meeeeeee eeee Meeeeeee Meeeeeeee[‌888‌]

Meeee eeeeeeeeeeeeee eeeeeee eeee eeeeee eeeeeeee eeeeeeeee eeeeeee e β-eeeeeee-eeeeeeee eeeeeeeee eeeeeee ee eee eeeeeee, eeeeeee 8,8-eeeeeee-8-eeeeeeeeeeeee[8.8.8]eeeeee [eeeeeee eeeeeee(eeeeeeeeeee-8,8-eeee)eeeeee],[‌888‌] eeeee eee eeee eeee ee eeeeee eeeeeeeee eeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeee, eee eee eeeeeeeeeeeeeeeeeeeeeeeeeeee (eeee = eeeeee, eeeee, eeee). Meee eeeeee eeeee ee eeeeeeee eeeeee eeeeeeee eee eeeeeeeee eeeee ee eeeeeeeeee: eeeeeeee > eeeeeee > eeeeee.[‌888‌] Meeeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeee, eee eee eeeeee eeeeeeee,[‌888‌] eeee eeee eeee eeee ee eeeeee eeeeeeeee ee eee eeeeeeee ee eeeeeee eee eeee eeeeeeeee.[‌888‌,‌888‌] Mee eeeee eeeeeeeeee ee eee eeeeeeeee MeeeeeeeMeeeeeeeMeeeee eeeeeeeee, ee eeeee eeeeeeeeeee eeeeee ee eeee ee eeeee ee eeeeeeee eeeeeeeeeeeeeee, eee eeee eeee eeeeeeee.[‌888‌]

Meeeee eeeee eeeeeeeee[‌888‌,‌888‌] eee eeeeeee eee eeeeeeeee eeeeeeeeeeeee[‌888‌‌888‌] eeeeee eeeeeeeee (eee eeeeeee) eeeeeee e eee β-eeeeeee-eeeeeeee eeeeeeeee. Mee eeeeeeeeeeee, eeeeeeee eeeeeeeeee eee eeee eeeee eeeeeeee eeee eee eeeeeeee eeeeeeee eeee eee eeeee ee eeeeeeeeeee; eee eeeeee eee eeeeeeee eeeeeeee eeeeeeeee eeeeeee eeeeeeeeee eeeeeee, ee eeeee ee eeeee eeeee eeee eeeeeeeee.

Meeeeeeeeeee Meeeeeeee

Meeeee Meeeeee (88, M8=Me; Meeee 88, Meeee 88); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeeeeee ee Me(MeMe)8eMeMM (888ee, 8.888eeee), (±)-MMMMM (888ee, 8.888eeee), eee 8-Å eeeeeeeee eeeeee (888ee) ee eeeeeee (8eM) eee eeeeeee ee 88°M eee 8e eee eeee eeeeee ee ee. MeMMM (888 μM, 8.88eeee) ee eeeeeee (8eM) eee eeeee, eeeeeeee ee eMeMM (8.8eM, 88.8eeee). Meeee 8e, eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee. MeMMM8 eeee (8eM) eee eeee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eee eeeeeee eee ee eeeeee eeeeeeeeeeeeee; eeeee: 888ee (eeeee).

Meeeee Meeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

M 8M eeee ee MeMe8 ee eeeeee (888 μM, 8.8eeee) eee eeeee eeeeeeee ee e eeeeeeeeee ee eeee 88 (88.8ee, 8.88eeee) eee eeeeeeeee 8-Å eeeeeeee eeeeeeeee eeeeee ee eeeeeeee MM8Me8 (8eM). Meeee 88eee, eMeMM (88 μM, 8.8eeee) eee eeeee. Meeee e eeeeeee 88eee, MeMMM (888 μM, 8.8eeee) eee eMeMM (888 μM, 8.8eeee) eeee eeeee; eeeee e eeeeeee 8e, eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee 8M ee MMe. Mee eeeeeee eee eeeeeeeee eeee Me8M eee eee eeeeeeee Me8M eeeeeeee eeee eeeee (Me8MM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eee eeeeeeee eee eee ee eeeeee eeeeeeeeeeeeee; eeeee: 888ee (88%).

8-Meeeeeeeeeee-8-eee (88):[‌888‌]

M eeee ee Me(Me)8Me8 (88ee, 8.8eeee) eee 8-eeeeeeeeee (888ee, 88eeee) ee eMeMM (88eM) eee eeeeee ee 88°M. Meeee 8e, eee eeeeeeee eee eeeeeee ee eeeeeeeeee. Mee eeee eee eeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee eeeeeee ee MMMM (eeeeee eee, eeeeee/MMMe8); eeeee: 888ee (88%).

References