Science of Synthesis

von Angerer, S., Science of Synthesis, (2005) 26, 65.

Examples for the use of elemental bromine (see Section ‌26.1.1.2.5.2‌) for the oxidation of alcohols are rare. Generally a base or other components are required for a successful reaction. The conversion of 1,2- and 1,3-diols into hydroxy ketones is readily achieved when treated with di- or tributyltin oxide and bromine.[‌175‌] It is understood that bromine cleaves the intermediate stannyl compounds to give the ketones. This reaction is used for the conversion of various 1,2- and 1,3-diols into the corresponding hydroxy ketones with the secondary hydroxy group as the preferred site of oxidation.[‌175‌–‌178‌] Most of these reactions are performed with protected[‌177‌] or unprotected glycosides. The conversion of 1-O-methyl­glucose (‌62‌) into its 3-oxo derivative ‌63‌ demonstrates the selectivity of this reaction (‌Scheme 40‌).[‌175‌]

‌Meeeee 88‌ Meeeeeeee Meeeeeeee ee 8-M-Meeeeeeeeeeee eeee Meeeeee ee eee 8-Mee Meeeeeeeee eee e Meeeeeeeee Meeeeeeeeeee[‌888‌]

Meeeeeeeee eeee eeeeeee eee eeee ee eeeeeeeee ee eee eeeeeeee ee e eeeeeeee. Me eeeeeee ee eee eee ee M-eeee-eeeee-8-eeeeeeeeeeeeeeeeeeeeeee, eeeee eeeeee eee eeeeeeeeee ee eeeeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeee ee eeee ee eeeeeeeee eeeeee.[‌888‌] Me eeeeeee ee eee eeeeeeeee ee eee eeeeeeeeeeeeeeeee ‌88‌ ee eee eee eeeeeeeeee ‌88‌ (‌Meeeee 88‌). Mee eee eeeeeeeeeeee ee eeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeee.

‌Meeeee 88‌ Mee Mee ee M-eeee-Meeee-8-eeeeeeeeeeeeeeeeeeeeeee ee Meeeeeee eee Meeeeeeeee ee Meeeeeee eeee Meeeeee[‌888‌]

Me eeeeeee ee e eeeeeeeeeee-eeeee eeeeeeeee eeeee ee eee eeeeeee-eeeeeeeee eee(eeee­eee)eeeeeee(M) eeeee, eeeee eeeeeeee eeeeeeee ee eeeeeee, e.e. eeeeeeeee ee eeeee­eeeeeeee (‌88‌), ee eeee eeeeee eeee e eeeeeeeee eeeeee ee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee eeeeeee (MMMMM) ee eeeeeee (‌Meeeee 88‌).[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeee ee Meeeeeeeeeeee eeee Mee(eeeeeee)eeeeeee ee Meeee Meeeeee ee eee Meeeeeee ee 8,8,8,8-Meeeeeeeeeeeeeeeeeee-8-eeee ee Meeeeeee[‌888‌]

Mee 8-(eeeeeeeeee) eeeeeeeeee ee 8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee ee eeee eeee eee eeeeeeeeee eeee eeeeee eeeeeee, e.e. eeeeeeeee ee 8-eeee-eeeeeeeeeeeeeeeeee (‌88‌) (‌Meeeee 88‌).[‌888‌,‌888‌] Meeeeee eeeeeeee eeeee eeeeee eeee eeee eeeeeee eeee eeeeeeeee eeee. 8-Meeeeee eee 8,8-eeeeeeeee eeeeee eee eeeeeeeee eeee eee eeeeeeeeeeeee 8-eee eee 8,8-eeeee eeeeee ee 88–88% eeeee. Mee eeeeee eee ee eeeeeeee eeee eeeeeeeeeee, eeeeeeeee ee eeee ee eeeeeeeeeeee, ee eeee ee eee eeeeeee.[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeeee ee 8-eeee-Meeeeeeeeeeeeeeee ee 8-eeee-Meeeeeeeeeeeeeeeee eeee Meeeee Meeeeee[‌888‌]

Meeeeeeeeeeee, eee eeeeeeeee ee eeeeeeee eeee eeeeee eeeeeee eee ee eeeeeeeee ee eee eeeeeee ee eee eeeeeeee eee ee eee eeeeeeee ee eeeeeee (‌Meeeee 88‌).[‌888‌,‌888‌] Mee eeeeeeee eee eeeeeee eeeeeeee eee eee eeeeee eee eeeeeeeee. Meeeeeeee eee eeeeeee ee eee eeeee eeeee ee eeeeeeeee eeee eeeeeee ee eeeeeeeee eeeeee ee eee eeeeeee ee eeeeeee. Meeeee eeeeeee eeeeeeee eeee eeeeee eeeeeeeee, eeeee eee eeeeeeee eeeeeeee eeeeee eeeeeee ee eeee, eee ee eeee eee eee eeeeeeeee eeeeeeeee ee eeeeeeeee eee eeeeee 8,8-eeeee ee eeeeeee eeeeeee eee/ee eeeeee.[‌888‌]

M-Meeee eeeeeeeee eeee ee M-eeeeeeeeeeeeee[‌888‌–‌888‌] eee M-eeeeeeeeeee­eeeee[‌888‌–‌888‌] eee eeee eee eee eeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeee. Me eeeeeee ee eeee eeee ee eeeeeeee ee eee eeeeeeeeeeeeee ee 8-eeeeeeeeeee-8-ee eeee 8-eeeeeeeeeee-8-eee (‌88‌) (‌Meeeee 88‌).[‌888‌] Meeeeee ee eee eeee eeeeeeee eeeeeeeeee M-eeeeeeeeeeeeee ee eeee eee eeeeeeeee eeeeeee eee eeeeeeeee eeeeeeeeee ee eeeeeee eeeeeeee.[‌8‌,‌888‌–‌888‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeeeeeee-8-ee ee 8-Meeeeeeeeee-8-eee eeee M-Meeeeeeeeeeeee[‌888‌]

Me eeeeeeeeeee ee M-eeeeeeeeeeeeee ee ee eeeeeeeee eeeee ee M-eeeeeeeeeeeeeeee,[‌8‌] eeeeeeee ee ee eeeeeeeee eeee eee eeeeeeeeeee eeeeeeeee. Me eeeeeeeeeee eeeeeeeeeee ee eeee eeeeeee ee eee eeeeeeeeee ee eeeeeeee eeeeeeee eeee eeeeeeeeee 8-eeeeeeeeeee eeeeeee, eeee ee eee eeeeeeeee ee 8-(eeeeeeeeeee)eeeeeeeeeeeeee (‌88‌) eeee eeeeeeee eeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeeee ee Meeeeee[8.8.8]eeeee-8-ee eeee 8-(Meeeeeeeeee)eeeeeeeeeeeeee ee Meeeeeeee eeee M-Meeeeeeeeeeeeeee[‌888‌]

Mee eeeeeeeee eeee M-eeeeeeeeeeeeeeee eee ee eeee eeeeeeeee eeee eee eeeeeeee ee eeeeeee eee ee eeeee ee eee eeeeeeee ee ee eeeeeeeee eeeeee ee β-eeeeeeeeeeee, e.e. eee eeeeeeeee ee eeeeeee (‌88‌) (‌Meeeee 88‌).[‌888‌] Meeee eeee eeeeeeee eeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeee, e eeee ee eeeeeeeee eeeeeee eeee eeeeeeeeeee eee eeeeeeee ee eeeeeee. Meeeeeeeeeee eee eeee eeeee eee eeeeee eeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeeeeeee ee eee eee ee M,M′-eeeeeee-M,M′-eeeeeeeeeeeee(8-eeeeeeeeeeeeeeeeee) eee eee eeeeeeeeeee ee eeee eeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeeeee ee Meeeeee ee Meeeeeeee ee Meeeeeeeee eeee M-Meeeeeeeeeeeeeee ee eee Meeeeeee ee β-Meeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeee ee Meeeeeeeee ee Meeeeee: Meeeeeeee ee Meeeee 8-Meeeeeeeeeeee-8-eeeee (‌88‌); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeee ee e eeeeee eeeeeeee ee eee eeee, eeeeee eeeeeeeee, eeeee, eee eeee. Meeeee eeeeeee eeeeee eeeeee eee eeeeeee eeeee ee eeeeeee eeee eeee eee eeee.

Mee eeeee eeeeeeeee ‌88‌ (8.8–8 e), (Me8Me)8M (ee. 8 eeeee), eee ee eeeeee ee 8-Å eeeeeeeee eeeeee ee MMMe8 (88–88 eM) eeee eeeeeeee eeeee eee eeeeeeeee eeeeeeeee eeeeeeeeee (8–8 e) eee eeee eeee eeeeee. Me eeee eeeeeee, Me8 (ee. 8 eeeee) eee eeeee ee 8°M eeee eeeeeeee eeeee eee eeee eee eeeeeee eeeeeee (8–8 eee). Meee, eee eeeeeee eee eeeeeee eeeeee eeee e eeeeee ee eeeeee eee. Mee eeeeee eee eeeeee eeeeeeeeee eeee MMMe8 ee eeeeee eee Me eeeeeeeee, eeee eeeeee eeee MeMMe ee eeeee eee eee eeeeeeeeee, eeeee eee eeeeeeeeeeee eeee eee eeeeeee eee; eeeee: 88%.

8-eeee-Meeeeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌888‌]

Meeeee M: M eeee ee 8-eeee-eeeeeeeeeeeeeeeee (8.88 e, 88 eeee) eee 8-(eeeeeeeeee)-8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeee (888 ee, 8.8 eeee) ee MM8Me8 (888 eM) eee eeeeeeee eeee ee 8% MeMMM8 (888 eM). Me eeee eeeeeeee eeeeeee eee eeeee eeeeeeeeeee MeMeM8•8M8M (88.8 e, 8.888 eee) eeee eeeeeeee eeeeeeee eee eeeeeee ee ee eee eeee. Meeeeeee eee eee­eeeeee eee ee eeeeeeeeee 8 e ee ee, eee eee eeeeeeee eee eeeeeeee eeee ee 8% MeMMM8 (8 eM). Mee eeeeeee eeeee eee eeeeeeeee eee eee eeeeeee eeeee eeeeeeeee eeee MM8Me8. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M, eeeee (Me8MM8), eee eeeeeeeee ee eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 88–88°M.

8-eeee-Meeeeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌888‌]

Meeeee M: Me eeeeeee (8 e) ee MM8Me8 (88 eM) eeee eeeee MeMeM8•8M8M (8.88 e, 8.8 eeee) eee eeee 8-eeee-eeeeeeeeeeeeeeeee (8.88 e, 8.8 eeee), eeee e eeeee eeeeee ee eee eeeeeee. Mee eeeeeee eee eeeeeee eee 88 e ee ee. Mee eeee eee eeeeeeee eeeeeee eeeeeeee eeeee eee eee eeeee eee eeeeeeeeee eeeeee eeee eee eeee eeeeeee ee Me8M (888 eM). Meeeeeeeeee ee eee eeeeeeee eeeeeeeee eeeee eeeeeee eeeeeeee eeee eee eeeee eeeeeeee ee eeeeee 888% eeeeee (MMM); eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8e, 888.
• 8.Meeeee-Meee, (8888) 8/8e, 888.
• 8.Meeeee-Meee, (8888) 8/8e, 888.
• 8.Meeeee-Meee, (8888) 8/8e, 888.