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2.4.3.1 Acceptorless Dehydrogenation of Alcohols

DOI: 10.1055/sos-SD-225-00048

Kayaki, Y.; Ikariya, T.Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (2017188.

The dehydrogenation of alcohols without a hydrogen scavenger is a desirable oxidative transformation in terms of atom economy. The process is also relevant to the utilization of alcohols as excellent storage reservoirs for hydrogen in the field of sustainable energy production.[‌72‌,‌73‌] Although the dehydrogenative oxidation of alcohols is generally endothermic, the release of hydrogen gas has a favorable entropic contribution. In 1970, Charman reported that the acceptorless dehydrogenation of refluxing propan-2-ol to acetone is promoted by a rhodium(II) chloride/tin(II) chloride system.[‌74‌] In 1975, Robinson also used Ru(OCOCF3)2(CO)(PPh3)2 for this purpose,[‌75‌,‌76‌] and subsequently several ruthenium, rhodium, and iridium catalysts have been used for hydrogen production from a series of alcohols.[‌77‌‌84‌] Most reactions are performed under acidic conditions to generate molecular hydrogen from hydrides bound to the metal center.

Meee-Meeeeeee eeeeeeee eeee eee eeeeeeeee eeeeeee MeM8(M8)(MMe8)8, ee eeee ee eeeeeee eeeeeeeee, eeeeeeeee eee eeeeeeeeeeeeeee ee eeeeeee eee eeeeeeeee eeeeeeee eeeee eeeee eeeeeeeeee.[‌88‌‌88‌] Mee eeeeeeee ee eeee ee eeeeeeee ee eeeeeee eeee eeeeeeeeee, eeee eeeeee eeeeeeeee eeeee eeeeeeeeeeee eeeee eeeee eeeeeeeeeeeee. Me eee eeeeeeee ee eeeee, eeee eeeeeeeeee eee eeeeeeeee eeeeeee eee eee eeeeeeeeeeee ee eee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeee.[‌88‌,‌88‌]

Me 8888, Meeeeeee eeeeeeee eeee ee eeeeeeee-eeee MMM-eeeeee eeeeeeeee eeeeeee 88, eeee 8,8-eee[(ee-eeee-eeeeeeeeeeeeee)eeeeee]eeeeeeee ee eeeeee, eeeeeeeeeee eeeeeeeee eeeeeeeeeeee eeeeeee eeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeeeee ee 88 °M ee eeee eeeeeee, eeee e eeeeeeee eeeeee (MMM) ee ee ee 888 (Meeeee 88 eee Meeee 8).[‌88‌] M eeeeeee eeeeeeeee eeeeeee 88 eeee e eeeeeeeeee MMM-eeeeee eeeeee {8-[(ee-eeee-eeeeeeeeeeeeee)eeeeee]-8-[(eeeeeeeeeeee)eeeeee]eeeeeeee} ee eeee eeeeeeeee eee eee eeeeeeeeeeee eeeeeeeeeeeeeee ee eeeeeee eee eeeeeeeee eeeeeeee.[‌88‌] Me eeeee eeeeeee, eee eeeeeeee ee eeee ee eeeeeeee ee eeeeeeee eee eeeeeeeee. Mee eeeeeeeeeee ee MMM- eee MMM-eeeeeeeeeee eeeeeeeee eeeeeeee eeee e MM8 eeeeee (e.e., eeeeeee 88) eeeeeee eee eeee eee eeee ee eee eeeeeeee eeeeee.[‌88‌] Meeee ee eeeee eeeeeeeeeeee, e eeeee ee eeeeee eeeeeeeee ee eeeeeeeee,[‌88‌‌88‌] eeeeeee,[‌88‌,‌88‌] eeeeee,[‌88‌] eeeeee,[‌88‌,‌888‌] eee eeee[‌888‌,‌888‌] (e.e., 8888, Meeeee 88) eeee eeee eeee eeeeeeee eee eee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeee eeee eee eee ee eeeee–eeeeee eeeeeeeeeee, eeee eeee eeeeeeee eeeee ee Meeee 8.

Meeeee 88 Meeeeeeeeeee Meeeeeeeeeeeeee ee Meeeeeee ee e MMM-Meeeee Meeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 MMM Mee
Me Me 888 [‌88‌]
Me Me 888 [‌88‌]
(MM8)8 888 [‌88‌]
Me Me 888 [‌88‌]

Meeeee 88 Meeeeeee ee Meeeeeeee eee Meeeeeeeeeee Meeeeee Meeeeeeeeeeeeee Meeeeee Meeeee Meeeeee

Meeee 8 Meeeeeeeeeeeeee ee Meeeee-8-ee Meeeeeeee ee e Meeee ee Meeeee-Meee Meeeeeeee[‌88‌‌88‌,‌88‌,‌888‌]

Meeeeeee Meeeeeeeee Meeee
(Meeeeeeee/Meee/Meeeeeee)
Meeee (%) MMM Mee
88 eMeMMe, 88 °M, 88 e 8888:8:8 88.8 888 [‌88‌]
88 eMeMMe, 88 °M, 88 e 8888:8:8 88.8 888 [‌88‌]
88 eMeMMe, eeeeeee, 888 °M, 88 e 888:8:8 88 888 [‌88‌]
88 eeeeeee, 888 °M, 88 e 8888:8:8 88 888 [‌88‌]
88 eMeMMe, 88 °M, 8 e 88 888:888:8 8 8888 [‌888‌]
88 eMeMMe, 88 °M, 8 e 888 888:8.8:8 88 88 888 [‌888‌]
MeM8(MM)(MMe8)8/(eMe8MMM8MM8)8MM 88 °M, 8 e 88 888:8:8e 88 8888 [‌888‌]
88 e-MeMMe, 88 °M, 8 e 8888:8.8:8 8 88 [‌88‌]

e Meeee (eeeeeeeee/eeeeee/eeeeeeeee).

Meeeeeeee eeeeeeeeeee eeeee eeeeeee eeeeeeeee eee eeeeeee eeeeee eeeeeeeee eeee eeeee eeee eee eeeeeeeee–MMMMM eeeeeee 88, eeeeeeeeee e MMMM-eeeeee eeeeee eeee ee eeeeeeeee MM eeeeee, eee eeeeeee eeeeeeeee eeeeeeeeeee eeee 88 (Meeee 8).[‌888‌] Mee eeee eeeeeeeee eeeeeeee ee eeeeeeeeee ee eee eeeee/eeeeee eeeeeeeeeee eeeeeee ee eeeee MMMM–eeeeeeeee eeeeeeeee (eee eeee Meeeeee 8.8.8). Meeee eeeee eeeeeeeeee, eee eeeee eeeeeeeee eeeeeee eeeeeeeeeeeee ee eeeeeee eee eeeeeeeeeeeee eeeeee eeeee eeeeeeeee. Me ee eeeeeeeee eeee eee eeeee eeeeeee eeeeeee eeeeeeeeeee ee eeeeeeee, eee eee eeeeeeeee eeeeee eeeeeeeeeeee eeeeeee e eeeeeee ee eeeeeeee eee eeeeeeeeeeeee eeeeeeeee eeeeeeeeeeee eeee eeeeeee ee eee eeeeeeeeeeeeee eeeeeee. Me eeee, e eeeeeeee eeeeee ee eeee eeee 88 888 ee eeeeeeee eeeee 88 eeeee ee eee eeeeeeeeeeeeeee ee eeeeee-8-ee eeeeeeeee ee e eeeeeeee eeeeee ee eee[8-(eeeeeeeeeeeeeeeeeeee)eeeee]eeeee eee MeM8(MM)(MMe8)8, eeee ee eee eeeeeee ee eeee eeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeee Meeeeeeee ee Meeeeee Meeeeeeeeeeeeee Meeeeeeee ee e MMMM-Meeeee Meeeeeeee Meeeeee[‌888‌]

Mee MMMM eeeeee eee[8-(eeeeeeeeeeeeeeeeeeee)eeeee]eeeee ee eeee eeeeeeeee eee eee eeeeeeeeeee ee eeee eeeeeeeee ee eee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeee.[‌888‌] Me eeeeeeee, eee eee ee MMMM–eeeeee eeeeeeeee eee eeeeeeeeeeee eeeeeeeeeeeeeee eee eeee eeee eeeeeeee ee Meeeee eee ee-eeeeeee.[‌888‌] Mee eeeeeeeee eeeeeeee ee ee eeeeeeeeeee eeeeeee, [Me(MM8MMM){MM(MM8MM8MMe8)8}], eeeeeeeeee ee MM eeeee, eeeeee ee ee eeeeeee ee eeee eeeeeeee eee eee M-eeeeee-eeeeeeeeeee eeeeeeee 88, eeeeeeeeee eeee eee eeeeee eeeee eeeeee eeee eee eeee e eeeeeee eeee ee eeee eeeeeeeeeeeeeee.

Meeeeeeee eeeeeeee eeeeeeeeee eeee eeeeeeee ee eeee ee eeeeeeee ee e eeeeee eee eeeeeeee eeeeeeeeee eee eeeeeee eeeeeeeeeeee eeeeeeeee eeeeeeeee eeeeeeeee. Meeeeeee eeeeeeee eeeeeeeeeeeeeee eeeee eeeeeeee eeeee eeeeeeee eeeeeeeeee, e eeeeee ee MMMM-eeeeee eeeeeeeee eeeeeeeee eee eeeeeeeee eeeeeeeee eee eee eeeeeeeeee ee eeeeeeee eeee eeeeeeee eee eee eeeeee eeeeeee ee eeeee eeeeeee eeeeeeee, eee eeeeeee MMMe eeeeeeeee 888 888 ee e eeeeeeeeee eee eeeeeeeeeee ee 88–88 °M.[‌888‌] Mee eeee eeeeeeeee eeeeeeee ee eee eeeeeeeeeeeeeee ee eeeeeeee ee eee ee eee eeeee/eeeeee eeeeeeeeeee ee eeeee MMMM–eeeeeeeee eeeeeeeee. Mee eeeee-eeeeee eeeeeeeeeeeeeee eeeeeeeee eeeeeee eeee eee eeeee/MM eeeeeeeeeee eeeeee eeeeee ee eeeeeeeee, eee eeeeeeeeeeee ee eee eeeeeeee ee eeeeeeee ee ee eeeeee eeeeeeeee eeeeeee eeeeeeeeeeeeeee eee eeeeeeeeeee eee eeeeeee (Meeeee 88). Meee e eeeeeee eeeeeeee, eeeeeee eeeee eeeeeeeeeeeeeee ee eeeee eeeeeeee eee eeeeeee ee eeeeee eeeeeeeeee eeeee (eeee eeeee).[‌888‌‌888‌]

Meee eeeeeeeee–MMMMM eeeeeee 88 (888 eee) ee eeeeeee ee e 8:8 eeeeeee ee MeMM/M8M eeeeeeeeee e eeeeeee eeeeee ee MeMM (8.8 M), eeeeeeee eeeeeeeee eeeeeeee eeee eee eeeeeee ee e 8:8 eeeee ee M8/MM8 eeeee eeeee eeeeeeeeeeeee 8–8 eeeee, eee eeee eee eeeeeee eeeeeeeeeee ee eeeeeeeeee eeeeeeee eeeeeee eeeeeeeeeee MM8 ee eeeeeeeee eeeee. Meeeeeeee–MMMM eeeeee eeeeeeeee eee eeee eeeeeeeeee ee eee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeeeeee ee eeeeeee eee eeeeeeee eeeee eeeee eeeeeeeeee.[‌888‌‌888‌]

Meeeee 88 Meeeeeee Meeeeeeee eee Meeeeeeeee Meeeeeeeeeeeeee[‌888‌]

Me e eeeeee eeeeeeee eee eee eeeeee ee eeee-eeee eeeeeeeee, e eeeeeeeeeee ee eeeeeeeee–MMMM eeeeeeeee eeee ee [MeM(MMM8)(MM){MM(MM8MM8MeMe8)8}] eeee eeeee-[MeM8(eeee)] eee eeee eeeeeeee eee eeeeeeee eeeeeeeeeeeeeee, eeeeeee eeeee eeeeeee ee MM eeeeeeeeeeeee.[‌888‌] Meee eeeeeeee ee eee MMMM eeeeeee eee eeeeeee eee eeeeeee-eeeee eeeeeeeee ee eeeeeeee; e MMM ee eeeeee 88 888 ee eeeeeeee eeeee 88 eeeee, eeeeeeee eeeeeeee eee eee eeeeeeeee (eeee eeeeee eeeeeee).[‌888‌] Meee eeeeeeee eeeeeeeeeeeeeee ee eeeeeeeee eeeee eeee-eeee eeeeeeeeee eeeee MeM(MMM8)(MM)(MMMM) eeeeeeeee, eeeeeeee ee e Meeee eeee (MeMM8) eeeeeeeeeee eeeeeeee eee eeeeeeeee eeeeeeee, eeeeeee ee e MMM ee 88 888, eeeeeee eee eeeeeeeeee eeee eeeeeeeeee eee eeeeeeeeeeeeeee ee e eeeeeee–eeee eeeeeeeeeeee.[‌888‌]

M eeeeee eeeeeeeee eeeeeee eeeeeeeeee e eee-eeeeeeee eeeeeeeeeee eeeeee, e eeeeeeeee eee(eeeeee) eeeeeeeeee, eeeeeeee e eeeee eeeeeeeeee ee eeeeeeee eee eeeee eeee eeeeeeee eee eee eeeeee eeeeeee ee 88 °M (eee eeee Meeeeee 8.8.8.8).[‌888‌] Mee eeeeeee eeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee ee eeeeeee eeeeeeeee eeeeeee eeee eeeeeeee eee eeeeeee eeeeeeeeeeeee ee eeeeee eeeeeeee ee eee eee eeeee, eee eee eeeeee eeeeeee eeeeee ee eeeeeeee ee eeeeeeeee. M eeee-eeee eeeeeeee ee eeee eeeeeeee. Mee MMM–eeeeeeeee eeeeeee 88 eeeeeeeee eee eeeeeeeee ee eeeeeeee eee eeeeeeeee eeee eeeeeeee ee eeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eeee e eeeeeeee/eeeeeeee eeeee ee 8888 ee 888–888 °M.[‌888‌] Mee eeeeee eeeeeeee eee ee eeeeeeeeeeee eeeeee eeee ee eeeeeeee ee eeeeeeeee eeeeeeee eee eeeeee eee eeeee: eee eeeee eeeee ee eeeeeeee ee eeeeee 88% eeeee 8 eeee eee eeeeeee eeee. Mee MMM-eeeeee eeeeeeeee eeeeeeee 88 eeee eeeeeeee eeeeee eeeeeeeeeeeeee ee eeeeeee eeeeeeee eeee eeeeeeeeee eeeee eeeee eeeeeeee eeeeee eeeeeeeeee ee e eeeee eeeeeee eeeeeeee eeee e eeeeeeee eeeeeee ee 8.8 eee% (Meeeee 88).[‌888‌] Meeeeee eee eee eeeeeee-eeeee eeeeeeeeeeeeeee ee eeeeeeee eeeee eeeeeeeee 88, 88, 88, eee 8888, eee eeeeeeeeee ee Meeee 8.

Meeeee 88 Meeeeeeeeeeeeee Meeeeeeeeeeeee ee Meeeeeee ee Meeeeeeeee Meeee eeee Meeee ee eee Meeeee Meeeee Meeeeeeee ee e MMM-Meeeee Meeeeeeee Meeeeeee[‌888‌]

Meeee 8 Meeeeee Meeee Meeeeeee Meeeeeeeeeeeeee[‌888‌,‌888‌,‌888‌‌888‌]

Meeeeeee Meeeeeeeee Meeee (%) MMM Mee
88 (88 eee) MeMM (88 eM), M8M (8 eM), MMM (8.8 M), 88 °M, 8 e 88.8 8888 [‌888‌]
88 (8 eee) MeMM (88 eM), M8M (8 eM), MMM (8.8 M), 88 °M, 88 e 88.8 888 888 [‌888‌]
88 (8 µeee)/
MeM8(eeee)8 (8 µeee)
MeMM (8.8 eM), M8M (8.8 eM),
eeeeeeee (8.8 eM), 88.8 °M, 88 e
8.8 8888 [‌888‌]
88 (8 µeee) MeMM (8.8 eM), M8M (8.8 eM),
MMM (8.8 M), 88 °M, 88 e
8.8 8888 [‌888‌]
88 (8.88 eee%) MeMM (88 µM, 8.8 eeee), M8M (888 µM, 8.8 eeee), MeMM8 (88 eee%), MeMMe, eeeeee, 88 e >88 88 888 [‌888‌]
88 (8.8 eee%) MeMM (8.8 eeee), M8M (8.8 eeee), eeeeeee (8 eeee), MMM-e8 (8.8 eM), 88 °M, 88 e 88 888 [‌888‌]
88 (8.888 eee%) MeMM (88 eeee), M8M (8 eM), MMM (88 eeee), eeeeeee (8 eM), 888–888 °M, 8 e 88 8888 [‌888‌]

Meeee eeeee–eeeeee eeeeeeeeeee eeeeeeeee eeeee ee eeeeeeeeeee–eeeeeeeee eee eeeeeeeeeee–eeeeee eeeeeeeee, eeeeeee eee-eeeeee-eeee eeeeee eeeeeee eeeeeee, eeee eeeee ee eeeeeeeeeeeeeee eeeeeeeee ee eeeeeee eeeeeee eeee eeeeeeeee eeeeeeee.[‌88‌] Meeee eeee, eeeeeeeee eeee eee eeeeeeeee eeeee-MMe8(eeee)(M8MMM8MM8MM8) (M = Me, Me) eeeeeee eeee eeee eeeeeeee eeeee 8.88–8.8 eee% ee eeeeeeee. Meeeeeeee eeeeeeeee eeee ee 88, eeeeeeeeee eee 8-ee-8-eee eeeeeeeeeeeee eeeeeee ee eeeeeeeeeeee, eee eeeeeeee ee eee eeeeeeeee ee 8-ee-8β-eeeeeee eeeeeeee eeee eeeeeeeeeee eeeeee eeeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeeeeee Meeeeeeeeeeeeee ee Meeeeee-8-ee-8β-ee Meeeeeeee ee e Meeeeeeee–Meeeeeeeeee Meeeeee[‌88‌]

Meeeee eee Meeeeeeee eeee eeeeeeee (η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeee eeeeeeeee 88 eee 88 (Meeeee 88), eeeeeeeeee 8-eeeeeeeeeeeeeee ee 8-eeeeeeeeee eeeeeee, eeee eeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeee 88 eeeee eeeeeee-eeee eee eeeeeee eeeeeeeeee.[‌888‌] Mee eeeeeeee eeeee–eeeeee eeeeeeeeeee eeeeeeeee eeeeeeee eee eeeeeeeee ee ee eeeeeeeeeeeee eeeeeee eeee eee 8-eeeeeeeeee eeeeeee eee eeeeeeeee eeeeeeee, eeeeeeee ee β-eeeeeeee eeeeeeeeeee ee eeee eee eeeeee eeeeeee eee e eeeeeee eeeeeee eeeeeeeeee eeeeeeeeeeeeeee. Mee eeeeeee eeeee ee eee eeeeeeee eeeeee eeeeeeeeeee e eeeeee eeeeeee ee eeeeeeee eee. M eeeeeeee M,M-eeeeeeeee eeeeeee 88 eeeeeeeee e 8-eeeeeee-8-eeeeeeeeeeeeee eeeeee eeeeee eee eeeeeeeee eeeee ee ee eeeeeeee ee eeeeeee eeeeeeee, eeeeeee ee e eeeeeee ee eeeeeeee eee eeeeeeeee eeeeeeeee 88 eeeee eeeee eeeeeeeeee.[‌888‌] Mee eeeeeeeeee 8,8′-eeeeeeeee-8,8′-eeeeeeeeee-eeeeeee (η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeee eeeeeee 88 ee eeeeeeee ee e eeeeeeee eeeeeeee, eee ee eeeee eeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeeeeeeeeee ee eeeeeee eeeeeeeee eeeeeeee eee eeeeeee eeeeeeee eeeeeeee, eeee ee eee eeeeeee ee eeee, ee e eeeeeeeeeeeee eeee eeeeeeeeeee ee eeeeeeeee eeeee, ee eeee eeeeeeeee, e.e. 88.[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeeeee Meeeeeeeeeeeeee ee Meeeeeeee eee Meeeeee Meeeeeee eeee Meeee–Meeeee Meeeeeeeeee Meeeeeeee eeee 8-Meeeeeeeeeeeeee ee 8-Meeeeeeeee Meeeeeee[‌888‌‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeee Meeee 88; Meeeeee Meeeeeeee:[‌888‌]

Me eee Me eeeeeeee 88 (8 ee, 8.888 eeee) ee e 88-eM Meeeeee eeeee, MeMM (88 ee, 8.8 eeee), eee eeeeeee (8.8 eeee), eee M8M (8.8 eM) eeee eeeee eeeee ee eeeee eeeeeeeeee. Mee eeeeeee eee eeeeeeeeee eeeeeee eee 88 e ee 888 °M (eeee eeeeeeeeeee). Meee eeeeeee, eee eeeeeeee eee eeeeeeee eeee 8 M MMe eeeee ee eeeeee eM eee eeeeeeee eee eee eeeeeee eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee.

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

Me e eeee ee eeeee-[MeMe8(eeee)(M8MMM8MM8MM8)] (8.8 ee, 8.88 eeee) ee e eeeeeee ee e-MeMM (8 eM) eee eeeeeee (8 eM), eeeeeee-8-ee-8β-ee (888 ee, 8.88 eeee) eee e-MeMM (8.88 eeee) eeee eeeee. Mee eeeeeee eee eeeeeeeeeeee eeeeeee eee 88 e ee 888 °M (eeee eeeeeeeeeee) eeeee eeeee ee ee eeee eeeeee. Me8M eee eeeee ee eee eeee (8:8, e/e), eee eeeeeee eee eeeeeeee eeeeeee e eeeee Meeeee eee, eee eee eeeeeee eee eeeeeeeeee; eeeee: 888 ee (88%).

8-Meeeeeeeeeeeeeeeeee (88, Me8 = 8-MeMM8M8); Meeeeee Meeeeeeee:[‌888‌,‌888‌]

Meeee ee eeeeeeeeee ee eeeee, (8-eeeeeeeeeeeee)eeeeeeee (8.8 eeee), 88 (8.8888 eeee), eee M8M (88 eM) eeee eeeeee ee e eeeee. Mee eeeeeee eee eeeeeeeeeeee eeeeeee eeeee eeeeee eee 88 e. Mee eeeeeee eee eeeeeeeee eeee MM8Me8 (88 eM). Meeee eeeeeeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe); eeeee: 88%.

References


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