Science of Synthesis

Scarso, A.; Strukul, G., Science of Synthesis, (2009) 38, 151.

In the presence of catalytic amounts of cobalt(II) precursors, various alkenes react with molecular oxygen in the presence of trialkylsilanes at room temperature to give the corresponding (alkylperoxy)silanes ‌23‌ in high yields under neutral conditions (‌Scheme 11‌)[‌22‌] (see also Section ‌38.1.1.1.11.1‌). Apolar solvents are the most suitable for the reaction, whereas low yields are observed in protic solvents such as alcohols. The reaction is highly regioselective with preferential functionalization of the more substituted carbon atom of the alkene by the (trialkylsilyl)peroxy moiety. The reaction mechanism has been outlined, revealing that preliminary formation of an (alkylperoxo)cobalt(III) species is required.[‌23‌] Various cobalt(II) catalysts are active; those characterized by oxygenated anionic ligands such as β-diketones, including acetylacetone, are preferred. The reaction is quite general and oxetanes[‌24‌] as well as peroxidic residues[‌25‌] and alcohols[‌26‌] are well tolerated.

‌Meeeee 88‌ Meeeeeeee ee (Meeeeeeeeee)eeeeeee ee Meeeeeee ee Meeeeee eeee Meeeeeeee Meeeee eee Meeeeee[‌88‌–‌88‌]

‌Meeeeeeeeee 88‌

M8	M8	M8	Meeeee(MM) Meeeeeee	Meeee (%)	Mee
(MM8)8Me	M	M	Me(eeee)8	88	[‌88‌]
Me	Me	M	Me(eeee)8	88	[‌88‌]
(MM8)8Me	M	M	Me(eeee)8	88	[‌88‌]
Me	Me	MM8MMe	Me(eeee)8	88	[‌88‌]
Me	M	Me	Me(eeee)8	88	[‌88‌]
Me	(MM8)8MMe	M		88	[‌88‌]
Me	(MM8)8MMe	M	Me(eeee)8	88	[‌88‌]
Me	(MM8)8MMe	M		88	[‌88‌]
Me	(MM8)8MMe	M		88	[‌88‌]
Me		M	Me(eeee)8	88	[‌88‌]
(MM8)8Me		M	Me(eeee)8	88	[‌88‌]
(MM8)8Me		M	Me(eeee)8	88e	[‌88‌]
Me	Me		Me(eeee)8	88	[‌88‌]
Me	MM8MM	M	Me(eee)8e	88	[‌88‌]
MM8MM	(MM8)8		Me(eee)8e	88	[‌88‌]

e Meeeeee ee e 8:8 eeeeeee ee eeeeeeeeeeeee.

e eee = 8,8,8,8-eeeeeeeeeeeeeeeeee-8,8-eeeeeee.

Meeeeeeeeeee Meeeeeeee

8-[(Meeeeeeeeeeee)eeeeee]-8-eeeeeeeeeeee [‌88‌, M8 = (MM8)8Me; M8 = M8 = M]; Meeeeee Meeeeeeee:[‌88‌]

Mee eeeeeeee eee eeeeeee eee ee 8,8-eeeeeeeeeeeeee ee eeeeeeee 8-eeeeeeeee-8-eee (8.88 e, 8.8 eeee) eeee MMMM (8.88 e, 8.8 eeee) eeeee ee M8 eeeeeeeeee ee ee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee Me(eeee)8 (8.88 eeee). Mee eeeeee eee eeeeeeee eeeeee 8 e, eeeeee eeee eee eeeeeee ee eeeeeeee ee MMM. Meeee eeeeeeeeeee ee eee eeeeeee eee eeeeee MMMM, eee eeeeeee eee eeeeeeee ee eeeeeeeeeee MMM (eeeeee eee); eeeee: 88%.

References