Science of Synthesis

Kirschning, A.; Gille, F.; Wolling, M., Science of Synthesis: Applications of Domino Transformations in Organic Synthesis, (2015) 1, 355.

General Introduction

The Brook rearrangement,[‌1‌–‌4‌] named after A. G. Brook (1924–2013), refers to the intramolecular 1,2-anionic migration of a silyl group from carbon to oxygen in α-silylated carbinols ‌1‌ in the presence of a catalytic amount of a base or alkali metal (‌Scheme 1‌). By deprotonation of the hydroxy group, the migration is accelerated. Occasionally, the reverse process has been reported, which is named the retro-Brook rearrangement. If after silyl migration the newly formed carbanion ‌2‌ is trapped by an electrophile other than a proton, Brook rearrangements will become part of a cascade process (‌Scheme 1‌).[‌5‌]

‌Meeeee 8‌ Meeeeee Meeeee ee eee Meeee Meeeeeeeeeeee eee Mee Meeeeeeee eeee Meeeeee Meeeeeeee[‌8‌]

Meeee eeeeeeeeee ee eee Meeee eeeeeeeeeeeee eee eeeee (e.e., eee- eee eeee-Meeee eeeeeeeeeeeeee) ee eeeee eeeeee ee eeeeeeeee ee eeeeeeee ee eeeeee, eeeeeeeeeeee, eee eeeee eeeee eeeeeeeeee eeeee eeeeee eeee eeeee (8,8- ee 8,8-Meeee eeeeeeeeeeeeee[‌8‌,‌8‌]). Mee 8,8-Meeee eeeeeeeeeeeee ee β-eeeeeeeee eeeeeeeee ‌8‌ (e = 8) ee eeee eeeeee eeeee ee eeee ee Meeeeeee eeeeeeeeeee,[‌8‌] eee eeeeeeeee eee eeeeee ee eeeeeee eeeeeeeee eeee eee eeeee ee eeeeeeee eee eeeeeeeeeeee eeeeeeeee ‌8‌ (e = 8) ee ee eeeeeeeeeeee eee eeeeee eeeeeeeeee (‌Meeeee 8‌). Mee eeeeeeeeeee eeeeeee e eeee-Meeeeeee eeeeeeee eeeeeee ee eeeeeeeeeeeee eee e eeeeeee eeeeeeee ee eeeeeee eeee eeeeeee ee eee eeeeee eeeeee. Meeeeeeeeeee, eee eeeeee ee eeeeeeee eee eeeeeeeeeeee ee eeeeeee eeeeeeeee eeeeeeeee ee 8,8-Meeee eeeeeeeeeeeee ee γ-eeeeeeeee eeeeeeeee ‌8‌ (e = 8) eeeeee eeeee ee 8,8-Meeee eeeeeeeeeeeeee, eeeeeee 8,8-Meeee eeeeeeeeeeeeee eee eeee eeee.[‌8‌,‌8‌]

Meeeeeeee eeeeee eeeeee eeeeeeeeeee ee eeeeeeeee eeeeeeeee ‌8‌ ee ‌8‌ eee eee eee ee eeeeeee eee eeeeeeeeeeee ee eeeeee Meeee eeeeeeeeeeeeee. Mee eeeeeee, eeeee eeeeeeeeeee eee eee eeee eeeeee eeee eeeeeeeeeeeee ee eeeeeeeee, eee eee eeee eeeeeeeee ee eeeeee ee eeeeeeeeeeee ee eeeeeeee eeeeeeeeee ee eeee eeeeeee ee eeeeeeee.

Meee eeeeeee eeee eeeee eee eeeee eeeeee: (e) eeeeeee eeeeeee ee eeeeeee eeeeeeeeee eeeeee ee eeeeeeeeee Meeee eeeeeeeeeeeeee ee eeee ee (e) eeeee eeeeeeeee ee eeeeee eeeeeeeee eeeeeeeee eeeeeeeeeeee ee eeeeeee eeeeeee eeeeeeeee.

References