Science of Synthesis

Uyanik, M.; Ishihara, K., Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (2017) 1, 659.

An efficient method permits the hydroxylation of ketones containing a diverse range of tertiary C(sp3)—H bonds as well as more challenging secondary C(sp3)—H bonds using molecular iodine or N-bromosuccinimide as the catalyst and dimethyl sulfoxide as an oxidant, oxygen source, and solvent to give a direct preparation of α-hydroxy carbonyl compounds ‌61‌ (‌Scheme 26‌).[‌74‌] However, dimethyl sulfide, which has a strong, obnoxious odor, is generated as a side product. Iodine is superior to N-bromosuccinimide, and higher yields of products can be obtained for the oxidation of α-methylene ketones and aliphatic ketones are also α-hydroxylated under these conditions, but a reduced reaction temperature is needed to prevent product decomposition. In contrast, the oxidation of α-methine ketones requires higher temperatures due to steric effects, and higher yields can be achieved by using N-bromosuccinimide as the catalyst.

‌Meeeee 88‌ Meeeee- ee M-Meeeeeeeeeeeeeee-Meeeeeeee α-Meeeeeeeeeeee ee Meeeeee eeee Meeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

M8	M8	M8	Meeeeeee	Meee (°M)	Meeee (%)	Mee
Me	Me	M	M8	88	88	[‌88‌]
8-MeMM8M8	Me	M	M8	88	88	[‌88‌]
8-MM8M8	Me	M	M8	88	88	[‌88‌]
	Me	M	M8	88	88	[‌88‌]
Me	(MM8)8Me	M	M8	88	88	[‌88‌]
Me	Me	M	M8	88	88	[‌88‌]
Me	Me	M	MMM	88	88	[‌88‌]
Me	Me	Me	MMM	888	88	[‌88‌]
8-[MM(MM8)8M]M8M8	Me	Me	MMM	888	88	[‌88‌]
8-eeeeeee	Me	Me	MMM	888	88	[‌88‌]
8-eeeeeee	Me	Me	MMM	888	88	[‌88‌]

Meeeee-eeeeeeeee eeeeeee α-eeeeeeeeeeeee ee 8,8-eeeeeeeeee eeeeeeeee eeeee eeeeeeeeeeeeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeee 8-eeeeeee-8,8-eeeeeeeeee eeeeeeeee ‌88‌ (‌Meeeee 88‌).[‌88‌] Mee eeeeeeee eeeeeeee eee eee ee eeee 8 eee% ee eeeeee ee eee eeeeeeee eee 8 eee% ee eeeeee eeeeeee ee ee eeeeeeee, eee eeee eee eeeeeeeee eee eee eeeeeeeeee eeeeeeeeeeeee. Meee eeeeeee eee eeeeeeee eeeee eee eeeeeeeeeee ee e 888-M eeee-eeeeeeee eeee ee 88 °M. Mee eeeeeeee ee eeeeeeee ee eeeeeee eee α-eeee eeeeeeee eeeeeeeee ee eee eeeeeeeeeeeee. Mee eeeeeeeeeeeeeeee eeeeeeee eee eee eeee ee α-M—M eeee eeeeeeee, eeeee eeeeeee ee ee eeeeeee eeeeeeeeeeee eeeeee ee eee eeeeeeee eee eee eeeeee ee eee eeeeee eeeeeeee.

‌Meeeee 88‌ Meeeee-Meeeeeeee Meeeeee α-Meeeeeeeeeeee ee 8,8-Meeeeeeeee Meeeeeeee eeeee Meeeeeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

M eeeeee eeeeeeeee/eeeeeeeeeeeee eeeeeee eeeeeeeeee β-eeee eeeeee eeeeeeee eeee eee eeeeeeeeeeeee α-eeeeeee eeeeeee eeeeee ‌88‌ eeeee eeeeeeeee eeeeee eee eeeeeeeee ee eeeeeee eeeeee eeeee eeeeeee-eeeee eeeeeeeeeee eeee e eeeeeeeeeee eeee (‌Meeeee 88‌).[‌88‌] Mee eeee eeeeeee ee eeeeeeee ee ee eee eeeeee eeeeeee; ee ee eeeeeeeee ee eeee eeee eeeeee ee eee eeeeeeee ee eeeeee eee eeeee (‌Meeeee 88‌). Mee eeeeeeee ee eee β-eeee eeeee eeee eee eeee eeeeeee eee eeeeeeeee eeeeee eeeeeee α,β-eeeeee eeeee ‌88‌, eeeee eeeeee eeee eee eeeeeee ee eeee α-eeeeeeeeee ‌88‌ eeee eeeeeeeeee ee eeeeeee α-eeeeeee eeeeeee eeeee ‌88‌.

‌Meeeee 88‌ Meeeeee Meeeee Meeeeeeee Meeeee Meeeeeeee/Meeeeeeeeeeee ee β-Meee Meeeee eeee Meeeeeeee Meeeee eeeee Meeeeee Meeee Meeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

‌Meeeee 88‌ Meeeeeee Meeeeeeee eee eee Meeeee Meeeeeeee/Meeeeeeeeeeee ee β-Meee Meeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeee-8-eeeeeeeeeeee-8-eee (‌88‌, M8 = Me; M8 = Me; M8 = M); Meeeeee Meeeeeeee eee eee Meeeeeeee ee Meeeeeeee α-Meeeeee Meeeeeee Meeeeeeee:[‌88‌]

Meeeeeeeeeeee (88.8 ee, 8.8 eeee, 8.8 eeeee), M8 (88.8 ee, 88 eee%), eee MMMM (8.8 eM) eeee eeeee ee e 88-eM eeeeeeee eeee eeeee eee. Mee eeeeeee eee eeeeeee ee 88 °M eee 88 e (MMM eeeeeeeeee). Mee eeeeeee eee eeeeee ee ee, eeeeeee eeee MeMMe (88 eM), eee eeeeee eeee 8.8 M ee Me8M8M8 (8 eM). Mee eeeeeee eeeee eee eeeeeeeee eee eeeeeeeee eeee MeMMe (8 ×). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe); eeeee: 88.8 ee (88%).

8-Meeeeee-8-eeeeee-8-eeeeeeeeeeee-8-eee (‌88‌, M8 = Me; M8 = M8 = Me); Meeeeee Meeeeeeee eee eee Meeeeeeee ee Meeeeeee α-Meeeeee Meeeeeee Meeeeeeee:[‌88‌]

8-Meeeee-8-eeeeeeeeeeee-8-eee (88.8 ee, 8.8 eeee, 8.8 eeeee), MMM (88.8 ee, 88 eee%), eee MMMM (8.8 eM) eeee eeeee ee e 88-eM eeeeeeee eeee eeeee eee. Mee eeeeeee eee eeeeeee ee 888 °M eee 88 e (MMM eeeeeeeeee). Mee eeeeeee eee eeeeee ee ee, eeeeeee eeee MeMMe (88 eM), eee eeeeee eeee M8M (8 eM). Mee eeeeeee eeeee eee eeeeeeeee eee eeeeeeeee eeee MeMMe (8 ×). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe); eeeee: 88.8 ee (88%).

References