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26.1.1.2.13 Method 13: Oppenauer Oxidation

DOI: 10.1055/sos-SD-026-00003

von Angerer, S.Science of Synthesis, (20052699.

In 1937, Oppenauer showed that steroidal alcohols can be oxidized with acetone in the presence of a tri-tert-butoxyaluminum catalyst.[‌374‌] An alternative catalyst for this type of oxidation reaction is aluminum triisopropoxide. The reverse process is known as the MeerweinPonndorfVerley reaction.[‌6‌] The alcohol and ketone form an equilibrium via a cyclic transition state which includes the catalyst and facilitates the hydride transfer from the alcohol to the oxidant (Scheme 94). Under the conditions of Oppenauer oxidations, functionalities such as C=C and CC bonds, amino groups, or halogens are not affected.[‌6‌,‌375‌] Usually, a large excess of acetone or cyclohexanone is used as the hydrogen acceptor and in many cases the product has to be removed by continuous distillation to shift the equilibrium towards the product side.

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Mee Meeeeeeee eeeeeeeee eee eeeee eeee eeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeee, eeee ee 888 (Meeeee 88).[‌8‌,‌88‌] Meee eeeeee eee eeee eeee eeee eee eee eeeeeeeee eeeeeeeeee ee eeeeeee eeee eeeeeeeee eeee eeeeeeeeee ee eee eeeeeee eeeeeeee.[‌888‌] Me ee eee eeeeeeeeee ee eeeeeee eeeeeeee, eee eee eeee eeeeeeeee ee e eeeeeee eeeeeeeee eee eee eeeeeeeeeee ee eeeeeee.

Meeeee 88 Meeeeeeee Meeeeeeee ee 8-Meeeeeeeeeeeeee ee 8-Meeeeeeeeee[88]

Meeee eee 8888e eeeeeee eeeee eeeeeeeee eeee eeee eeeeeeeeee eeeee eee ee eeee eee eee eeeeeeeeee ee eeeeeeeee eeeeeeee eeee eeeeeee, eeee eeeeeeee eeeeeeeee ee eee eeeeeeee. Meeee eeeeeeee eeeeeee eeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeee eeee 8-eeeeeeeeeeeeeeeee ee eee eeeeeee eeeeeeee (Meeee 88, eeeee 8),[‌888‌] eeeeeeeee eeeeeeeee eeee eeeeeee ee eee eeeeeee (Meeee 88, eeeee 8),[‌888‌] eeeeeeeee(MM) (Meeee 88, eeeeeee 8 eee 8)[‌888‌,‌888‌] ee eeeee­ee(MM) (Meeee 88, eeeee 8)[‌888‌] eeeeeeeee ee eeeeeeeeeee eeee eeeeeee, eee eeeeeee ­eee(eeeeeeeeeeeeeeeee)eeeeee ee eee eeeeeeee ee eeeeeeeeeee (Meeee 88, eeeee 8).[‌888‌] Mee eeeeeeeee eeeeeeee eee eeee ee eeeeeeeee eeeeeeee ee ee eeeeeee eeeeeee eeee eeeeeee ­(Meeee 88, eeeee 8).[‌888‌] Meeee eeeeeeeee eee ee eeeeeee eee e eeee eeeeee eeee eeeeeee eeeeeeeee(MM) eeeee ee eeee ee eee eeeeeeee (Meeee 88, eeeee 8).[‌888‌] Meeeeeee ee eeeeeeeee eee eeeeeeee eeee ee eee eeeeeeeee ee eeeeeee 888 eee eeeeeeeee ee Meeee 88.

Meeee 88 Meeeeeeee-Meee Meeeeeeeee ee Meeeeeeee Meeeeeee ee Meeeeee[888-888]

Meeee Meeeee 888 Meeeeeee Meeeeee Meeeeeeeee Meeee (%) Mee
8 eeeeeeeeeeeeee [(eMeM)8Me][MM8MM8] 8-M8MM8M8MMM ee, 88eee 88 [‌888‌]
8 eeeee-8,8(88)-eeeee-8,88-eeeeee Me(Me-Me)8 (88eee%) Me8MMMM (8 eeeee) MM8Me8, 8-Å eeeeeeeee eeeeee, 88°M, 88e 88 [‌888‌]
8 8-eeeeeeeeee­eeeeeeee eeeeeee MeM8 eeeeeee (eeeeee) eeeeeee, 88°M, 88e 88 [‌888‌]
8 eeeee-8-eee MeMe8(MMe8)8 (8.8eee%) eeeeeee (eeeeee) M8, M8MM8 (88eee%), eeeeeee (8.8% M8M), ­eeeeee, 88e 88 [‌888‌]
8 eeeee-8-eee-8,88-eeeeee MeMe8(MMe8)8 (8eee%) eeeeeee (eeeeee) M8, M8MM8 (88eee%), eeeeeee (8.8% M8M), ­eeeeee, 88e 88 [‌888‌]
8 eeeee-8-eee [MeMe(eee)]8 (8.8eee%), MMMe (88.8eee%) eeeeeee (eeeeee) M8, Me8MM8 (8 eeeee), M8M, 88°M, 8e 88 [‌888‌]
8 eeeeeeeee (M8M8)8MMM (8eee%) e-MeMMM (8 eeeee) eeeee, MeMM8 (8 eeeee), eeeeeee, ee, 8e >88 [‌888‌]
8 eeeeeee-8-ee-8-eee eeeeeee (eeeeee) eeeeeee (8 eeeee) M8, MMe8, ee, 88e 88 [‌888‌]
8 8-eeeeeeeeeee-eee-88-eee eeeeeee (eeeeee) MeMMM (8 eeeee) M8, MMe8, 88°M, 88e 88 [‌888‌]

e Mee eeeeeeeee eee 88β-eeeeeeeeeeee-8,8-eeee-8-eee.

e Mee eeeeeeeee eee 8β-eeeeeeeeeeee-8-ee-88-eee.

e 8,8-Meeeeeeeeee-8,8-eeeeeeeeeeee eeee eeeeeeeeeee eeee.

Me eeeeeeeeeee eeeeeeeeeeee ee eee Meeeeeeee eeeeeeeee ee eee eeeeee eeeeeeeeee ee eee Meeeeeee eeeeee 888, eeeeee ee eee eeeeeeee ee eeeeeeeeeeeeee eeeeeee eeee (8M)-eee-8-eeee, eeee (8M)-eee-8-ee-8-eee (888) eeee eeeeeeeeeeee, ee eeeeeee eeeeeeee, ee eee eeeeeee (Meeeee 88).[‌888‌]

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

Meeeeeeeeeeeeeee eeeeeeeeeeeee eee eeeeeeee eeeeeeeee eeee eeee eeeeeeeee eeeeeeeee. Meee eee eeee ee eeee eee eee eeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeee.[‌888‌] Mee eeeeeee ee eee eeeeeeeeee ee 8,8-eeeeeeeeeeee-8-ee-8-ee-8-ee eeee eee eeeeeeeeeeeee eeeeee ee 88% eeeee eeee eeeeeeeee eeee eeeeeeeee ee 88°M ee eeeeeee.[‌888‌]

Mee eeeeeeeee eeeeeeeee eee eee ee eeee ee eeee eeeeeeeeeeee eee eeeeeee eeeeeeee. Meee eeeeeeeee eeeeeeee eee eeeeeee eeee 8 eeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee eee eeeeeeeeeeeee eeeeeee eee eeeeeeee ee eeeeeeeeee eeeeee.[‌888‌] Meeee eeeee eeeeeeeeee eeee eeeeeeeee eeeeeeee eee eeeeeeeee eeee eeeeeeee eeeeeeeee, ee eee eeee eeeeeeeeeeee eee eee eeeeeeeee eeeeeeeeee ee eeeeeee-8,8-eeee eeee 8-eeeeeeeeeeeee-8-eee (888) (Meeeee 88).

Meeeee 88 Meeeeeeee ee Meeeeee-8,8-eeee ee 8-Meeeeeeeeeeee-8-eee eeee Meeeeeeeeeeeeeeeee Meeeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee 888 ee Meeeeeeee Meeeeeeee; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee eee eeeeeee eeeeeee (8.8eee) eee eeeeeeeeeeeee (888eM) ee eee eeeeeee (8.8M) eee eeeeee ee eeeeee eeeeee ee M8M ee eeeeeeeeee eeeeeeeeeeee. Meee Me(MeMe)8 (88.8e, 8.88eee) ee eee eeeeeee (888eM) eee eeeee eee eeeeeeeeeeee eee eeeeeeeee eee 8e. Meeee eeeeeee, eee eeeeeee eee eeeeeee eeee eeeeeee (MMMMMMM: eeeeeeeeee) eee eeeeee eeee eee M8MM8, ee MeMMM8, eee M8M. Mee eeeeeee eeeee eee eeeeeeeee ee eeeee eeeeeeeeeeee. Mee eeeeeee eeeeeeeeeeee ee eee eeeeeee eeeee eee eee eeeeeeeee eeee Me8M. Meeee eeeeeee eee eeeeee, eee eeeeeee eee eeeeeee eee eee eeeeeee eee eeeeeeee eeee eee eeeeeee.

Meeee-8,8(88)-eeeee-8,88-eeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee 88β-eeeeeeeeeeee-8,8-eeee-8-eee (888ee, 8.88eeee) ee MM8Me8 (88eM) eee eeeee eeeeeee (8.888eM, 8eeee) eee eeeeeee eeee eeeeeeee, eeeeeee eeeeeeeee 8-Å eeeeeeeee eeeeee (888ee) eee eee eeeeeee eee eeeeeee eee 88eee. Mee eeeeeeee eee eeee eeeeeee ee eee eeeeeeee ee Me(Me-Me)8 (8.888eM, 8.88eeee) eee eeeeeeeee ee MMM. Meeee eeeeeeee eee 88e, eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee 88% MMe (8eM). Mee eeeeeee eee eeeeeeee, eee eeeeeee eeeee eeeeeeeee, eee eee eeeeeee eeeee eeeeeeeee eeee MM8Me8 (8eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8), eeeeeeee eeee Meeeee (8.8e), eee eee eeeeeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeee­eeeeee (eeeeee eee, MeMMe/MM8Me8 8:8, Me 8.88); eeeee: 888ee (88%); ee 888888.8°M.

Meeee-8-eee-8,88-eeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

M eee-eeeeee eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeeee eee e eeeeeeee eeeeeeee eee eee eeeeeee eeee 8β-eeeeeeeeeeee-8-ee-88-eee (888ee, 8.888eeee), MeMe8(MMe8)8 (8.8ee, 8.8888eeee), eee M8MM8 (8.8ee, 8.8888eeee), eee eeeeee eeee M8 eee 88eee. Meeeeee (8eM, eeeeeeeeee 8.8% M8M) eee eeeee eeee e eeeeeee. Mee eeeeeeeee eeee eee ­eeeeeeee eeee eeeeeeee eeeee M8 eee 88e. Mee eeeeeee eee eeeeee eee eee eeeeeee eee eeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/Me8M 88:8) ee eeee eee eeeeeee; eeeee: 88ee (88%).

Meeeeee-8-ee-8-eee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

Me eeeeeee (~8e, Meeee M-888, eeeeeee, eeeeeeeeee) ee e eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeeee eee eee eeeee, eeeee M8, MMe8 (8eM) (MMMMMMM: eeeee), eeeee eeee eeeeeee-8-ee-8-ee (8% ee eeeeee). Meeee eeeeeeee eee 88eee ee ee, eeeeeee (8 eeeee) ee MMe8 (8eM) eee eeeee eee eeeeeeee ee ee eee eeeeeeeee eee 88e. Mee eeeeeee eee eeee eeeeeeee ee eeeeeee eeeeeee Meeeee eee eeeeee eeee MM8Me8 (88eM). Mee MM8Me8 eeee eee eeeee (MeMe8) eee eee eeeeeee eee eeeeeeeeee ee eeeee ee eeeee eee eeeeeee, eeeee eeeee ee ­eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeeeeeeee; eeeee: 88%.

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

M eeee ee eeeeeee-8,8-eeee (8.888e, 8.88eeee) ee MM8Me8 (88eM) eee eeeeeee eeee Me+MM8 (8.888e, 8.88eeee) eeeee M8 ee 88°M eee 8e. Mee eeeeeee eee eeeeee eeee eee ee MeMMM8 eeee eee eeeeeee eee 88eee. Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (88eM). Mee eeeeeee eeeee eee eeeee (Me8MM8) eee eeeeeeeeeeee ee eeeee, eeeeeeeee ee e eeeee eeeeee ee eee eeeeeee (MMMMMMM: eeeeeeeeee) eee eeeeeee ee e eee eeeeee ee eeeeee eee (88e, Meeeeee 88). Mee eeeeee eee eeeeeeeee eee eeeeeee ee eeeee ee 88°M eeeeeeeee. Meeeeee eeee eeeeeee eeeeeee Me8MM eee Me8MMM. Meeeeee eeeeeee eeee MeMMe eeeeeeee eee eeeeeee; eeeee: 8.888e (88%).

References


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