Science of Synthesis

Vil’, V. A.; Bityukov, O. V.; Terent’ev, A. O., Science of Synthesis Knowledge Updates, (2019) 3, 389.

The problem of the selectivity in the formation of geminal bishydroperoxides (see Section ‌38.11.2‌) was first solved by using ketals or enol ethers as starting reagents in reactions with hydrogen peroxide. Synthetic approaches that have been reported for the preparation of geminal bishydroperoxides ‌23‌ from ketals ‌22‌ include the use of tungstic acid (H2WO4),[‌71‌] boron trifluoride–diethyl ether complex,[‌72‌,‌73‌] and phosphomolybdic acid [H3Mo12O40P•xH2O] as catalysts (‌Scheme 11‌).[‌74‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee Meeeeeeeeeeeeeeee eeee Meeeeee eee Meeeeeee Meeeeeee[‌88‌–‌88‌]

‌Meeeeeeeeee 88‌

M8	M8	M8	M8	Meeeeeeeee	Meeee (%)	Mee
(MM8)8		Me	Me	M8MM8, M8M8 ee MeMM, MeMM	88	[‌88‌]
(MM8)8		Me	Me	M8MM8, M8M8 ee MeMM, MeMM	88	[‌88‌]
(MM8)88		Me	Me	M8MM8, M8M8 ee MeMM, MeMM	88	[‌88‌]
Me	Me	Me	Me	M8MM8, M8M8 ee MeMM, MeMM	88	[‌88‌]
Me	(MM8)8Me	Me	Me	M8MM8, M8M8 ee MeMM, MeMM	88	[‌88‌]
	Me	Me	Me	M8MM8, M8M8, MMM	88	[‌88‌]
(MM8)8		Me	Me	MM8•MeMM, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)88		Me	Me	MM8•MeMM, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)8		Me	Me	MM8•MMe8, M8M8 ee Me8M, Me8M	88	[‌88‌,‌88‌]
(MM8)8		Me	Me	MM8•MMe8, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)8		Me	Me	MM8•MMe8, M8M8 ee Me8M, Me8M	88	[‌88‌]
Me	eMe	Me	Me	MM8•MMe8, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)8Me	(MM8)8Me	Me	Me	MM8•MMe8, M8M8 ee Me8M, Me8M	88	[‌88‌]
		(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]
		(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)8MMM8M≡MM	Me	(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]
(MM8)8MMMM	Me	(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]
	Me	(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]
	Me	(MM8)8		M8Me88M88M•eM8M, M8M8 ee Me8M, Me8M	88	[‌88‌]

Mee eeeeeeee ee eeeeeee eeee eeeeeeee eeeeeeee eeeeeeeee ee eeeee eeeeeeeeeee–eeeeeee eeeee eeeeeee eeeeeeeeee eeeeeeee eee eeeeeeeee ee eeeeeeeeeeee ‌88‌ ee eee eeeee eeee. Meeeeeeeeeee eeeeee ee eeeeeeee eeeeeeee ee ‌88‌ eeeeeee ee eeeeee eeeeeeeeeeeee ‌88‌, eeeee eeeee eee eeeeeee ‌88‌ eeee eeeee eeeeeeeeeee. Mee eeeeeeee ee eeeeeee ‌88‌ eeee eeeeeeee eeeeeeee eeeee ee eee eeeeeee eeeeeeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee eee eee Meeeeeeee ee Meeeeee Meeeeeeeeeeeeeeee eeee Meeeeee Meeee Meeeeeee Meeeeeee eee Meeee Meeeeeeeeee–Meeeeee Meeee Meeeeee[‌88‌]

Meeeee eeee eeeeee ‌88‌ eee eeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeee ‌88‌ ee eeee eeeeee eeeee eeeeeeeee ee eeeee eeeeeeeeeee–eeeeeee eeeee eeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee Meeeeeeeeeeeeeeee eeee Meee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee ee Meeeeeee Meee Meeeeeeee:[‌88‌]

88% ee M8M8 (88 eM, 88 eeee) eee eeeeeeeee eeee MeMe eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee ee. 88 eM, eeeeeee eeee MeMM (88 eM), eeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeee ee e eeeeee ee 88 eM (ee eeeeee eeee ee eee Me8M), eee eeee eeeee (Me8MM8) eee eeeeee ee 8 °M. Mee eeeee ‌88‌ (8 eeee) eee eeeeeeeeee ee e eeeeeee ee eeee eeee (8 eM, ee. 88 eeee ee M8M8), eeeeeeee ee M8MM8 (8 eeee). Mee eeeeeeeee eeeeeeeeee eee eeeeeeeee eeee eeeeeeee eee eeeee eee eeeeeee eee 88–88 e ee 8 °M. MM8Me8 (88 eM) eee M8M (88 eM) eeee eeeee eee eee eeeeee eeee eeeeeeeee. Mee eeeeeee eeeee eee eeeeeee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeee eeeeee eeee eeeeeeee eee eeeeee eeeeeeeeeeee eeee eee. ee MeMMM8 (88 eM) eee eee. ee MeMe (88 eM) eee eeee eeeee (Me8MM8). Meeeeeeeeee eeeee eeeeeee eeeeeeee eeee ee eee, eeeee eee eeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeeee/Me8M).

Meeeeee Meeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee ee Meeee Meeeeeeeeee–Meeeeee Meeee Meeeeee Meeeeeeee:[‌88‌]

Me eeeee eeee ee M8M8 ee Me8M eee eeeeeeee ee eeeeeeeeee ee 88% ee M8M8 eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eeee ee eee Me8M, eee eeee eeeee (MeMM8) eee eeeeeeeeeeee eeeeeeeeeeeeee.

M eeee ee eeeee ‌88‌ (88 eeee) ee Me8M (88 eM) eee eeeee eeeeeeee eeee ee. 8 eee ee e eeeeeee eeee ee M8M8 (8.8–8 eeeee) eee MM8•MMe8 ee MM8•MeMM (8.8–8.8 eeeee) ee Me8M (88 eM) ee 88–88 °M. Mee eeeeeeeee eeeeeee eee eeeeeee eeeee eee eeeee ‌88‌ eee eeee eeeeeeeeee eeeeeeee (8–8 e; eeeeeeeeee ee MMM). Meee, M8MM8 (8 eeeee) eee M8M (88–88 eM) eeee eeeee eee eee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8.8–8 e. Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeee eeeeeeeee eeeee/Me8M 88:88 ee 88:88 eeeeeeee).

Meeeeee Meeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee ee Meeeeeeeeeeeeee Meee Meeeeeeee:[‌88‌]

M eeeeeee ee e eeeee ‌88‌ (8.8 eeee), e ee. 8 M eeee ee M8M8 ee Me8M (8 eM, 8 eeee), eee eee eeeeeeeeeeee eeeeeeeee eeeeeeeeeeeeeee eeee eeeeeee (M8Me88M88M•eM8M; 8 ee, ee. 8.88 eeee) eee eeeeeee ee eeeeeee eeeeeeeeeee eee 8 e. Me8M (88 eM) eee eeeee, eeeeeeee ee M8M (8 eM). Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeee-eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee ee eeee eeee M8M (8 × 88 eM) eee eeeee (8 × 88 eM), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee ee eeeeee eeeeeeeeeee (MMMMMMM: ee eeeeeee). Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe).

Meeeee Meeeeee Meeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee e eeeeee eeee eeeee ‌88‌ (88 eeee) ee Me8M (88 eM) eee eeeee eeeeeeee ee ee. 88 °M eeee e eeeeee ee eeeee 8 eee ee e eeeeeee eeee eeeeeeeeee M8M8 (8.8–8 eeeee) eee MM8•MMe8 (8.8–8.8 eeeee) ee Me8M (88 eM). Mee eeeeeee eee eeeeeee eeeee eeeeeeee eeeeeeeeee ee eee eeeeee eeee eeeee ‌88‌ (8.8–8 e) eee eeeeeeee, ee eeeeeeeeee ee MMM. M8MM8 (8 eeeee) eee M8M (88–88 eM) eeee eeee eeeee, eee eee eeeeeeeee eee-eeeee eeeeee eee eeeeeee eee 8.8–8 e. Mee eeeeeee eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeee eeeeeeee eeee eee eeeeeee eeeee, eee eee eeeeeeee eeee eee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeee eeeeeeeee eeeee/Me8M 88:88 ee 88:88 eeeeeeee).

References