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23.14.1.1.7 Method 7: Wolff Rearrangement of Diazo Ketones

DOI: 10.1055/sos-SD-023-00535

Tidwell, T. T.Science of Synthesis, (200623585.

The Wolff rearrangement is a very useful method for the preparation of ketenes, usually with in situ capture, and is the subject of a comprehensive review.[‌79‌] In concentrated solutions, the ketenes formed can react intermolecularly with the diazo ketone precursors. For example, photolysis of the neat diazo ketone 87 to gives tert-butylketene; this reacts with the starting material 87 to give the lactone 88 (Scheme 27).[‌80‌] This reaction can be prevented by the use of a nucleophilic solvent or other trapping agent that captures the ketene before intermolecular reaction with the precursor occurs.

Meeeee 88 Meeeee Meeeeeeeeeeee eeee e Meeee Meeeee[‌88‌]

Me ee eeeee eeeee ee eee eeeeeeeeeeeeeee ee eee Meeee eeeeeeeeeeeee, ee eeeeeeeee eeeeee eeee eeeeeeeee eee eeeee ee eeee eeeeeee eeeeeee eeeee eeeeee eeeeeeeee, eee eeee eeeeeeee eeeeeeeee eeeeeeee eeeeeeeeeeee eeeeee ee eeeee eee eeeeeeeeeeeee.[‌88‌] Mee eeeeee eeeee eeeeeee Meeee eeeeeeeeeeeee ee eee eeeeeeeee eeeeee eeeeeeeeeee eeeeee 88 ee eeee eeeeeeeeeee eeeee e eeeeee 88 eeee eeeeee eeee eeeee ee eeee eee eeee 88, eeeeeeeeeeeee eeee eeeeeeeee ee eeeeeeeeeeeee (Meeeee 88).[‌88‌] Meeee eee eeee eeeeeeee ee Meeee eeeeeeeeeeeeee ee eeeee eeeeeee eeeeeee eeee eeeeeeeee eeeeee α-eeeee eeeee eeee eeee eeeee eeee eee eeeeeeee eeeeeeeee ee eeeeeeeeeeeee (eee Meeeeeee 88.88.8.8.8.8 eee 88.88.8.8.8.8).

Meeeee 88 Meeeeeeeeeeeeee ee e Meeeee(M) Meeee Meeeeee Meeee Meeeeeeeeeeee Me Meee e Meeeeeeeeeeeeee[‌88‌]

Mee eeeeee eee eeeeeeeee Meeee eeeeeeeeeeeee ee eee eeeeeeeee eeeeee eeeeeeeeeee eeeeee (M)-88 eeeee e eeee eeeeee ee eeeeeeeee ee eeeeeeeeeeeee ee eeeeeee ee eee eeeeeeeeeeee eeeeee eeee eeeee ee eeeeeeee,[‌88‌] eee eee eeeeeeeeeee eeeeeee eeeeeeeeeeeee ee (M)-88 ee eeee eee eeeeeeeeeeeee eeeeee (M)-88 eeeeeee ee eeee eeee 88% eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeee eeeee (M)-88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeeeeee ee e Meeeeee Meeee Meeeeeeeeeeee[‌88‌]

References