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25.1.2.2.2 Variation 2: Oxidation with Activated Dimethyl Sulfoxide and Related Species

DOI: 10.1055/sos-SD-025-00010

Podlech, J.Science of Synthesis, (20072533.

Utilization of dimethyl sulfoxide as the oxidant in the presence of a suitable electrophilic activator is one of the most frequently used methods for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively.[‌2‌,‌6‌,‌55‌‌58‌] Although some of the information given here has been gained from the syntheses of ketones, it relates to aldehydes as well. Two general features of all variations of this method are that no overoxidation to carboxylic acids is observed and diols are oxidized to 1,2-dicarbonyl compounds rather than cleaved oxidatively [as may occur when chromium(VI), manganese(VII), or ruthenium oxidants are employed]. Moreover, these variants use inexpensive and commercially available reagents and work both on small and large scales. Although many activation methods are recommended, only a fraction give constantly good results and these are the ones in common use. The first of them is the Swern method that traditionally employs oxalyl chloride as the activating agent. Acetic anhydride, trifluoroacetic anhydride, sulfur trioxidepyridine, and others find occasional application in this role as well. The CoreyKim method using dimethyl sulfide/N-chlorosuccinimide is included in this section since it and the Swern approach proceed through an identical intermediate. A comparison of the most frequently applied Swern-like methods has been published; however, the results obtained may be biased since they refer to the oxidation of just one substrate (decan-1-ol) (see Table 1).[‌59‌] Problems that occur with some of the methods are incomplete conversion, the formation of acetoxy- or chloro-substituted side products, and the generation of varying amounts of Pummerer products; the latter arise especially at higher temperatures. In addition, as the foul-smelling byproduct dimethyl sulfide is formed in all of the procedures, the reactions should be carried out in well-ventilated hoods and the solvent waste should be treated with bleach.

Meeee 8 Meeeeeeee ee Meeee-8-ee eeee Meeeeeee Meeeeeeee ee Meeeeeee Meeeeee ee eee Meeeeeee ee Meeeeeeee Meeeeeeeee Meeeee[‌88‌]

Meeeeeeeee Meeeeeeeee Meeeee (%) Mee
Meeee Me(MM8)8MMM Me(MM8)8MM Me(MM8)8MMM8MMe Meeee Meeeeeeeee
Me8M MMMM, 88°M, 88e 88 8.8 88 8.8 [Me(MM8)8MMe] [‌88‌]
MM8ee MMMM, 88°M, 8.8e 88 8.8 8.8 e.e. [‌88‌]
Me8M MMMM, 88 ee 88°M, 8.88e 88 88 88 e.e. [‌88‌]
eeeeeeee eeeeeeee MMMM/MM8Me8, 88 ee 88°M, 8.8e 88 88 8.8 e.e. [‌88‌]
(MMMe)8 MM8Me8, 88°M, 8.88e, eeee Me8M, 88°M, eeee ee 88 8.8 8.8 8 [Me(MM8)8Me] [‌88‌]
MMMM MM8Me8, 88 ee 88°M, 8.8e 88 e.e. 8 88 [Me(MM8)8M8MMM8] [‌88‌]
MMM/MMM eeeeeee, 88°M, 8.8 ee 88 8.8 8.8 8 [Me(MM8)8Me] [‌88‌]

e e.e.=eee eeeeeeee.

e MMMM eee eeeeeee.

Mee eeeeeeee eeeeeeee eeeeeeeee eeeeeeeee eeeeee (MeeeeeeeMeeeee eeeeeeeee) eeee 8,8-eeeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeeeee eeeee[‌88‌] eee, eeeeeeee eeee ee eee eeeeeeeee ee eee eeeeeeee eeeeeeee eee ee eeeeeeee eee e eeee eeeee ee eeeeeeeeee eeeeee (eeeeeeeee eeee-eeeeee eeee-eeeee eeeeee) eee eeeeeeeeee eeee eee eeeeeeeeee,[‌88‌] ee ee ee eeeeee eeeeeeeee eeee eee eee eeeeeeeee ee eeeeeeee. Mee eeeeeeee eeee ee ee eeeeeeeee eeee eeee eeeeeeeeeee. Meeeeee, eeeeeeeeee ee eee eeeeeeeeeeee eeee e eeee eeee (e.e., eeeeeeeeee eeee, eeeeeeeeeeeeeee eeee, ee eeeeeeeeeeeeee eeee) ee eeeeee, eeeee eeee eeeee eeee eee eeeeeeee ee e eeee ee eeeeeeee eeeeee eeeeee. Meeeee 8,8-eeeeeeeeeeeeeeeeeeeeeeee ee eeeeeeeee ee eeeeeee e eeeeeeeeee eeeeeeee eeee eee, eeeee eee eeeeeeeee, eeee ee eeeeeeeeeee ee eeeeeee eeeeeeeee eeee eeeeee eeee, eeeee eeeee ee eee eeeeeeeee ee 8,8-eeeeeeeeeeeeeeee, eeeeee eeeeeee, eee eeeeee eeeeeeee. Meeeeeeeeeeee, eee eeeeeeeeeeeeeeee, eee eeeeeeeeeee eeeeeee ee (eeeeeeeeeeeeee)eeeeee eeeeee eeee eee eeee eeeeee, eeeeeeee eeeeeeeee eeeeeeeeee. Mee eeeeeeeee ee 8,8-eeeeeeeeeeeeeeee eee ee eeeeeee ee eeeee eeee eeeeeeeee eeeeeee-eeeee ee eeeee-eeeeeee eeeeeeeeeeeee {e.e., M-[8-(eeeeeeeeeeeee)eeeeee]-M-eeeeeeeeeeeeeeeee eeeeeeeeeeeee, MMM}.[‌88‌] Meeeeeee, eeee eeeee eeeee eeeeeeee e eeeeeee eeeeeee eeeeeeeee eeeeeee eee ee eeeeeeee; eeeeee, eeeeeeee eeeeeeee ee eee eeeeeeeee eeee eeeeeeee eeeeeeeeeeeeeeeeeeeeeeee.

Mee Meeee eeeeeeeee, eeeee eeeeee eeeeeeee ee eee eeeeeeeeee eeeeeeeeeeee, ee eee eeee eeeeee eeeeeee ee eee eeeeeeee eeeeeeeee eeeeeeeee-eeee eeeeeeeee.[‌88‌,‌88‌‌88‌] Meee eeeeee ee eeeeeeeee, eeee ee eeeeeee [88, M8=(MM8)8Me] (Meeeee 88),[‌88‌,‌88‌] eee eeeeeeee eeee eeee eeeeee eee eee eeeeeeee eee eeeeeeeeeee eee eeeeeeee. Mee eeeeeee eeeeeee, ee ee eeeeeeeeeeee ee eeeeeee eeeeee eeeeeeee eeeee ee eee. Mee eeee eeeeeeee eeeeeeee eee eeeeeeeeeeeeeee eee eeeeeeeeeeeeeee, eee eeeeee eeee eeeeee eeeeeeee eee eeee ee eeee.[‌88‌] Meeeeeeeeeee ee eee eeeeee eeeeeee eeee eeeeeeee eeeeeeeee eee eeeeee eeeeeeee ee eeeeeeeee ee eee eeeeeeeeeee (eeeeeee eeeeeee 88 ee 88°M) eee eee eeeeeee ee eeeee ee eeee ee ee e eeeeeeee eeeeee eeeeeeeeeee. Meeeeeeeeeee, eeeeee eeeeeeee eeeeeeeeeeee eee eeeeeeee ee eeeeeee eee eeeeeeeeee ee eeee eeeeeeee eeeeeeeeee (eee eeeeeeeeee-8-ee,[‌88‌] Meeeee 88); eeeeeee, eeeeeeee eeeeeee eeeeee eee eeeeeeee ee ee 88°M, ee eeeeee eeeeeeeeeeee (8°M) eee eeeee eeeee eeeeeeeeeeeee.[‌88‌] Mee eeeeeeeee ee eeeeeeeee ee eeeeeeeeeeeee eee eeeeeeeee eeeeeeeeeeee ee eee eeeeeeee ee ee eeeee eeee (eeeeeeeee eeeeeeeeeeeee), eeeee ee eee eeeeeeeeeee. Meee eee eeee eeee ee eeee eeeeeeeeeeeeeeeeeee ee ee α-eeeeee eeeeeeee ee eeeeee, eee eeee eeeeeee eee eeeeeeee ee eeeeeee.[‌88‌] Mee eeeeeee, eeeeeeee eeeeeeeeeeeeeeee eeee 8-(eeeeeeeee)eeeeee-8-ee ee eeeeeeee eeeee eeeeeeee eeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeee eeee eeeee 8% eeeeeeeeeeee eeee eeeeeeeeeeeee ee eeee ee e eeee,[‌88‌] eeee eeeeeeeeeeee ee eeeeeeeeee eeee M,M-eeeeeeeeeeeeeeeeeeeee ee eeee eeeeeee.[‌88‌] Meeee eee eeeeeeeeeeeeee eeeeeeeeee (MM, MM8, eee MMM) eee eeeeeeee eee eeee eeeee eeeeeee (<8%) ee (eeeeeeeeeeeeee)eeeeee eeeeee eee eeeeee ee e Meeeeeee eeeeeeeeeeeee, eeeeee ee eeeeeeeeeeeee eeeeee. Meeeeeee ee eeeee eeeeeee, eee Meeee eeeeeeeee ee eee eeeeeeee eeeeeeeeee ee eeeeee eeeeeee.[‌88‌] Meee ee eeeeeeeeeee ee eee eeee-eeeeeeee eeeeeeeee ee 8-eeeeeeeeeeeeeeeee ee eee eeeeeeee (Meeeee 88).[‌88‌,‌88‌] Meeeeeeee eeeeee ee eeeeeeeeee eee eeeeeeeeeeee eeeeeeeee eeee eeeeeeeee eeeeeeeeee eee eeeeeeee. Me eeee eeeee, eeeeee eeeeeeeeeeeeeeeee ee eeeeeeeeeee ee e eeeeeeeeee eee eeeeee eeeeeeee. Meee ee eeeeeeeeee eeeeeeeee ee eee eeeeeeeee ee 8-eeeeeeeeeeeee eeeee eeeeeeee eeeeeeeee/eeeeee eeeeeeee eeeee eeee e 88% eeeee ee eee eeeeeeee eeeeeeee ee e 88% eeeee eeee eeeeeeee eeeeeeeee/eeeeee eeeeeeeeeeeeeeeee ee eeee.[‌88‌]

Meeeee 88 Meeee Meeeeeeee ee Meeeeee Meeeeeee eeee Meeeeeee Meeeeeeee/Meeeee Meeeeeee/Meeeeeeeeeeee[‌88‌,‌88‌,‌88‌,‌88‌]

Meeeeeeeeee 88

M8 Meeeee (%) Mee
MMM Meeeeeee
(MM8)8Me 88 88 [‌88‌,‌88‌]
(MM8)8Me 88 88 [‌88‌,‌88‌]
(MM8)8Me e.e. 88e [‌88‌]
(MM8)88Me e.e. 88 [‌88‌]
(MM8)88Me e.e. 88e [‌88‌]
e.e. 88 [‌88‌,‌88‌]
Me 88e e.e. [‌88‌,‌88‌]
MM8Me e.e. 88 [‌88‌,‌88‌]
e.e. 8888 [‌88‌,‌88‌]

e e.e.=eee eeeeeeee.

e Meeeeeeeee ee eee 8,8-eeeeeeeeeeeeeeeeeeeeee.

e Mee eeeeeee eee eeeee ee eee eeeeeeeee eeeeee eeeeeee ee 88°M.

e Mee eeeeeeeeeee eee eeeee ee eee eeeeeeeeeee ee 8-eeeeeeeeeeeee eee eee eeeeeeeee.

Me eeeeeeeeeeee eeeeeeeee eeeeeeeee ee eee eeeeeeee eeeeeeeee eeeeeeeee eeeeeeee eeeeeeeeeeeeeee eeeeeeeee ee eee eeeeeeeeee eeeeeee.[‌88‌] Meee eee, eee eeeeeeee ee e eeee ee eeeeee eee eeeeeeeeee eee eeeeeeeee eeeeeeeeeeee eeee eee eeeeeeee. Meeee eeee eeeeeeeee eee eee eeeeee eeeeeeeeeeeeeeeeeee eeeee ee eee eeeeeeee ee eee eeeee (eee eee eeeeeeeee ee ee ee 88% ee eeeeeeeeeeeeeeee ee eee eeeeeeeee ee eeeee-8-ee, Meeee 8, eeeee 8), eeee eeee ee eeeeeeeee ee eee ee ee eeee eeee 88°M (eeeeee 88°M) ee ee eeeeeeeeee eeeeeee (eeeeeeeeee eeeeeeeeeeeeeee).

Mee eeeeeeeeeee ee eeeeee eeeeeeeee ee ee eeeeeeeeee eeeee (eee MeeeeeeeMeeeeee eeeeeeeee ee eee Meeee eeeeeeeee) ee e eeee-eeeeeeeeeee eeeeeeeee eeee eeeeeeee eeee eeeeeeeeeee eeeeeeee; ee ee eeeeeeee eee eeeee-eeeee eeeeeeeee.[‌88‌] Meeee eeee ee eee eeeeeeeeee eeeeeeeee eeeeeeeee, ee eeee ee eeeeee eee eeeeeeeeee ee eee eeeeeeee. Meeeeeeeeeeee, eee eeeeeeeee ee eee eeeeee eeeeeee ee eeee eeee, eeee ee eeee eeeeeeeeeee, eeeeeeee eeeeeeeeeeee ee eeeeeeee eeee eee eeeeeeeee ee eeeeeeeee ee eeee eeeeeeee.[‌88‌] Meeeeeee, eeeeeeeeeee eeeeeee ee (eeeeeeeeeeeeee)eeeeee eeeeee (ee ee 88%)[‌88‌] eee eeeeeeee (eeee eeeeeeeeee eeeeeeee eee eeeeeee)[‌88‌] eee eeeeee ee eeeeeeeeee. Meeee eeeeeee eeeee eee eee ee eeee eeeeeeeee ee eeeeeee eeeee eeee.

Mee MeeeeeMeeeeee eeeeeeeee ee eeeeeee eeeeeeee, e eeeeeeeee eeee eeee eeeeee eeeeeeeeeeeeeeee eeeeeee ee ee eeeeeeeeee eeeeeee,[‌88‌] ee eeeeeeeeeeee eeee eee, eeeeeeee eee eeeeeee ee eeeeeeeeee eeeeeeeee, eee eeeeeeeee eee eeeeeeeeee: eee eeeeeeee ee eeeeeee eee ee eeee eeeeeeeeeee, ee eeeeeeeee eeeeee ee eeeeeeee, eee eeeeeee eeee eeeeee eee ee eeeeeeee. Meee, eee eeeeeee, eeeeeeee eeeeeee ee eeeeeeee ee eeeeeeeeeeeeee ee ee eeeeee eeeeeeeeeeee eeeee.[‌88‌] Meeeee ee (eeeeeeeeeeeeee)eeeeee eeeeee eee eeeeee,[‌88‌] eee eeeee eeeeeeeeeeeeeeeeeee α ee eee eeeeeeee eeeee ee e eeeeeeeee eeeeeee, ee eee ee eeeeeee eeeeeeeeee.[‌88‌] Meeeeeee ee eeee eeee ee eeeeeeeee eee eeeee ee Meeeee 88.[‌88‌‌88‌] Meeeeeee, eeee eeeeeeee eee eeee eeee ee eeeeeee eeeeeee eeeeeeeee eee eeeeee 88-eeee eeee ee eee eeeeeee eeeeeeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee Meeee Meeeee MeeeeeeeMeeeeeee Meeeeee[‌88‌‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
88 [‌88‌]
88 [‌88‌]
8888e [‌88‌,‌88‌]
88 [‌88‌]

e Meee 8.8% eeeeeeeeeeee.

Meeeee 88 Meeeeeeee ee e Meeeee Meeeeeeeeeeeee Meeeeee Meeeeee eeee Meeeeeee Meeeeeeee/Meeeee Meeeeeee/Meeeeeee[‌88‌]

Meeeeeeeee eeeeeee eeee eee ee eeeeee ee eeeeeee eeeee eeeeeee eeeeeeeeee eeee eeeeeeee eeeeeeee,[‌88‌] eee(eeeeeeeeeeeeeee) eeeeeeeee (eeeeeeeeeee),[‌88‌] ee eeeeeeeeee eeeeeeeee (Meeeeee eeeeeeeee).[‌88‌] Me eee eeeeeeee eeee, eee Meeeeee eeeeeeeee eeeeeeee ee eeee, eeeee eeeee eeee eeeeeeeeeeee (88°M) eeeeeeeee; eeeeeee, eeee eeeeeeeeeeeee ee eeeee eee eeeeeeee eeeeeeee ee eeeee eeeeeeeeeeee (8°M).[‌88‌,‌88‌]

Me eeeeeeeee, eeeeeeeeee ee eeeeeeee eeeeeeeee eeee eeeeeeee ee eeeeeeee eee, eee eeeeee eeeee eee eeeeeeeeeeee eeee eeee eeeeeee, eeeeeeee eeeeeee eeeeeee ee eee eeeeeeeee ee eee-eeeeeeeeeee.[‌88‌] Mee MeeeeMee eeeeeeee[‌88‌] eeeee eeeeeeee eeeeeee eee M-eeeeeeeeeeeeeeeee ee eeeeeee eeeeeeee ee eeeeeeeee 88 eeeeeeeeeee eeee eeeeeeeeeeeeeee (Meeeee 88).[‌88‌‌88‌] Meee eeeeeeeee ee eeeeeee eeeeeeeeee eeeeee eee eeeeeee ee eeeeeeee eeeeeeeee eeeeeeeee eeeeeee eeeeeee ee eee eeeeee eeeeeeeeeeeee eeee eee ee eee Meeee eeeeeeee. Meeeeee eeeeee ee eeee eeeeeeeee eee eeeeeee eeeeeeee eeee eeeeeee ee eeee ee eee eeeeeee.[‌88‌] Me eeee ee eeeee eeee eeeeeee eeeeeeee eee eeeeeeeee eeee eeeee eeeeeeeee ee eeeeeeee eeeeeee eee M-eeeeeeeeeeeeeeeee, eee eeee α,β-eeeeeeeeeee eeeeeeeee.[‌88‌] Meeeeeeeee eeee eeeeeeeeeee eeeeeee eee M-eeeeeeeeeeeeeeeee eee ee eeee eee eee eeeeeeeee eeeeeeeee ee eeeeeee eeeeeeee ee 8°M (eeeee eee eeee eeeeeee eeeeeeeeeee eeeeeeeeeee eeeeeeee eeeeeeeee eeeeeeee ee 88°M); eee eeee eeeeeeeeeee ee ee eeeeeeeeee eeeeee eeee eee eeeee eeee eeeeeeeee eee eeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeee eeee Meeeeeee Meeeeee/M-Meeeeeeeeeeeeeeee[‌88‌‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
(MM8)8Me 88 [‌88‌]
88 [‌88‌]
88e [‌88‌]
88 [‌88‌]
MM8Me(Me)8Me 88 [‌88‌]
(MM8)8MeMe8 88 [‌88‌]

e Meeee eeee eee eeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeee eeeee, eeee eeeee eee eeeeeee eee eeeeeeee ee eeeeeeeee eeee eeeeee eeeeeeeeeee ee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

Meeeeee [88, M8=(MM8)8Me]; Meeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeee/Meeeee Meeeeeee:[‌88‌,‌88‌]

M eeeeeee ee MMMM (88.8e, 888eeee, 88.8eM) ee MM8Me8 (88eM) eee eeeee ee e eeeeeee eeee ee eeeeee eeeeeeee (88.8e, 888eeee, 88.8eM) ee eeeee MM8Me8 (888eM) eeeee eeeee ee 88°M (MMMMMMM: ee ee eeeeeeeee eeee eee eeeeeeeeeee ee eeee eeeee 88°M eeeeee eee eeeeeeee). Mee eeeeeeee eee eeeeeeeee ee eee eeeeeeeee ee eee. Meeee eeeeeeee eee 88eee ee 88°M, e eeee ee eeeee-8-ee (88.8e, 888eeee, 88.8 eM) ee MM8Me8 (88eM) eee eeeee, eee eeeeeeeeeee ee eee eeeeeee eeeee eeee eeeee 88°M. Meeee eeeeeee eeeeeeee eee 88eee ee 88°M, Me8M (88.8e, 888eeee, 88.8eM) eee eeeee, eeeee eee eeeeeeeeeee eee eeeee eeee eeeee 88°M. Meeeeeeeee, eee eeeeeee eee eeeeeee ee eeee ee ee, M8M (888eM) eee eeeee eeeeeeee, eee eeeeeeee eee eeeeeeeee eee 88eee. Mee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8×888eM) eee eee eeeeeeee eeeeeeee eeee eeeee (Me8MM8). Meeee eeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeeeee; eeeee: 88.8e (88%); ee 8888°M/88Meee.

(8M,8M,8M,8M)-8-(Meeeeeeeeeeeeeee)-8,8-eeeee-8,8,88-eeeeeeeee-8-(eeeeeeeeeeeeeee)eeeee-8-eeee (88); Meeeeee Meeeeeeee Meeee Meeeeeee Meeeeeeee/Meeeee Meeeeeee:[‌88‌]

MM8eeeeeeee eeeeeee (88.8e, 8.88eee) eee eeeee ee eeeee eeeeeeee ee 8-eee eeeeeeeee ee e eeeeeee ee (8M,8M,8M,8M)-8-(eeeeeeeeeeeeeeee)-8,8-eeeee-8,8,88-eeeeeeeee-8-(eeeeeeeeeeeeeee)eeeee-8-ee-8-ee (88.8e, 8.88eee), eeeee MMMM (888eM), MM8Me8 (888eM), eee Me8M (88.8eM, 8.88eeee) ee 8°M. Meeee 8e, eee eeee eeeee eeeeeee eee eeeeeee eeee Me8M (8.8M), eeeeee ee eeee eeee M8M (8×888eM) eee eeeee (88eM), eee eeeee (MeMM8). Mee eeeeeee eee eeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 8:8); eeeee: 88.8e (88%). Mee eeeeeee eee ee. 88% eeee ee 8MMMM.

Meeeeee [88, M8=(MM8)8Me]; Meeeeee Meeeeeeee Meeee Meeeeeee Meeeeee/M-Meeeeeeeeeeeeeeee:[‌88‌]

MMM (8.8eM, 8.8eeee) eee eeeee eeee eeeeeeee ee MMM (888ee, 8.8eeee) ee eeeeeee (88eM) eeee ee 8°M eeeee eeeee (e eeeeeeeee eeeeeeeeeee eeeeeeee eeeeeeeeeee). Mee eeeeeee eeeeeee eee eeeeee ee 88°M eee eeeee-8-ee (888ee, 8.8eeee) ee eeeeeee (8eM) eee eeeee. Meeee eeeeeee eeeeeeee ee 88°M eee 88eee, e eeee ee Me8M (888ee, 8.8eeee) ee eeeeeee (8eM) eee eeeee. Mee eeee eeee eee eeeeeee eee, eeeee eeeeeee 8eee, Me8M (88eM) eee eeeee. Mee eeeeeee eeeee eee eeeeeeeee eee eeeeee eeeee eeee 8% ee MMe (8eM), eee eeee eeee M8M (8×88eM). Meeee eeeee eeeee (MeMM8), eee eeeeeee eee eeeeeeeeee eeee eee eeeeeee eeeee ee eeee e eeeeeeeee eeeee; eeeee: 888ee (88%).

References