Science of Synthesis

Tidwell, T. T., Science of Synthesis, (2006) 23, 587.

In the photochemical Wolff rearrangement, the products of Wolff rearrangement with capture by nucleophiles are configurationally stable. The photochemical Wolff rearrangement of optically active diazomethylpentanone (S)-‌92‌ in methanol gives the ketene (S)-‌93‌ that reacts with methanol to give the ester (S)-‌108‌ with 94–100% retention of configuration (‌Scheme 34‌).[‌83‌] The photochemical Wolff rearrangement is used for the preparation of monoalkylketenes, such as sec-butylketene (‌93‌)[‌83‌] and cubylketene (‌110‌): in the latter case, the ketene, obtained from diazo ketone ‌109‌, is captured by water to form the corresponding carboxylic acid ‌111‌ (‌Scheme 34‌).[‌92‌]

‌Meeeee 88‌ Meeeeeeeeeeeeeee ee Meeeeeeeeeeee Meeee Meeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeeeee Meeee eeeeeeeeeeeee ee eee eeeee eeeeee ‌888‌ eeeeeeee ee e eeee eeeeeee eeeeeee eee eeeeee eeeee eeeee eee eeeeeeeeeeeee eeeeee ‌888‌, eeeee ee eeeeeeee ee eeeee ee eeee eeee ‌888‌ (‌Meeeee 88‌).[‌88‌] Mee eeeeee eee eeee ee eeeeeeee ee ee eeeee ee eeeeeeeeeeeeee eee ee e eeeeeeeeeeeeeeee eeeee ee eeeee-8-eeeeeeeeee.[‌88‌]

‌Meeeee 88‌ Meeeeeeeeeeeeee Meeeeeeee ee Meeee Meeeeeeeeeeee ee e Meee Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee Meee (‌888‌); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Mee eeeee ee eeee eeeeeeee eeeeee ee eeeeeeeee eeeeee e eeeeee eeeeee. Meeeeeeeeeee ee eeeeeeeee ee eeeee, eeeeeeee, ee eeee, eee ee eeeeee eeeee ee eeeeeeeeee.

Meeeee eeeeeeee (8 eM) eee eeeee eeeeee ee e eeee ee eeeeeeeeeeeeeeee eeee (8.8 e, 88.8 eeee) ee MM8Me8 (88 eM). (MMMMMMM: eee eeeeeeee ee eeeeeeeeee.) Meeee eee eeeeeeeee eee eeeeee, eee eeeeeee eee eeeeeeee eee 88 eee. Mee eeeeee eeeeee eeeeeeee eee eeee eeeeeee ee 8.8 Meee eee ee, eeeeeee eeeeeee. Me8M (88 eM) eee eeee MM8M8 ee Me8M (8.8 eeee, 888eM) eeee eeeee, eee eee eeeeee MM8M8 eee eeeeeee eeeee e eeeeee ee M8. Mee eeeeeee eee eeeeeeeeee ee ee ee eeeee e eeeeee eeeee eeee eeeeeee eeeeeeeeeeee eee eeeeeeeee ee MMM (888 eM). M8M (88 eM) eee eeeee, eee eee eeee eee eeeeeeeeee eeeeeee Meeee eee 8 e eeee e eeeeee-eeeeeeee Me eeee. Mee eeeeeee eee eeeeeeeeee, eee eee eeeeeee eee eeeeeeeee ee MeMMe (888 eM). Mee eeee eee eeeee eee eeeeeeeeeeee ee eeee e eeeeeee eeee eee eeeeeeeeeeeeee (eeeeee) ee eeee e eeeeee-eeeeeeee eeeee; eeeee: 8.8 e (88%); ee 888–888°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88-8, 8888.