Science of Synthesis

Sankararaman, S., Science of Synthesis, (2008) 43, 442.

The conversion of an aldehyde by chain extension into an alkyne via the formation of a 1,1-dibromovinyl derivative is known as the Corey–Fuchs reaction[‌24‌] {‌Scheme 11‌; see also Science of Synthesis, Vol. 27 [Heteroatom Analogues of Aldehydes and Ketones (Section ‌27.24.1.2.2‌27.24.1.2.2)]}. The aldehyde is converted into the corresponding 1,1-dibromo derivative by reaction with carbon tetrabromide and triphenylphosphine, either with or without zinc. The dibromovinyl derivative is treated with a strong base, such as butyllithium or lithium diisopropylamide, to yield the alkyne. The intermediate acetylide can be protonated (e.g., to give ‌19‌), or either silylated or alkylated by quenching the reaction with an alkyl bromide or chlorotrimethylsilane (e.g., to give ‌20‌) prior to workup.

‌Meeeee 88‌ Meeee–Meeee Meeeeeeee ee Meeeeee[‌88‌,‌88‌]

Mee eeeeeee ee eee Meeee–Meeee eeeeeeee eee eee eeeeeeeee ee eeeeeeee ee eeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeee ‌88‌ eeee eee eeeeeeeeeeeee eeeeeee(eeeeeeeeeeee) eeeeeeeeee ‌88‌ ee eeeeeeeee eeeee ee eeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeee–Meeee Meeeeeeee ee e Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Mee-8-eee [‌88‌, M8 = (MM8)8Me]; Meeeeee Meeeeeeee:[‌88‌]

8,8-Meeeeeeeee-8-eee (8.888 e, 8 eeee) ee MMM ee −88°M eee eeeeeee eeee 8.88 M MeMe ee eeeeeee (8.8 eM, 8.8 eeee). Meeee eeeeeeee ee −88°M eee 8 e, eee eeeeeee eee eeeeeee ee eeee ee 88°M eee eeeeeeeeee ee eeee eeeeeeeeeee eee 8 e. Meeeeee eeeeee eee eeeeeee eeeeeeeeee, eeeeeeee ee eeeeeeeeeeee, eeee eee-8-eee; eeeee: 8.88 e (88%).

8,8-Mee[(eeeeeeeeeeeeee)eeeeeee]eeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

Me 8,8-eee(8,8-eeeeeeeeeeee)eeeeee (8.8 e, 8.8 eeee) ee MMM ee −88°M eee eeeee 8.8 M MeMe ee eeeeee (8.8 eM, 8.8 eeee) eee eee eeeeeee eee eeeeeee ee −88°M eee 8 e. Me eee eeeeeeee eeee MMMMe (8.8 eM, 8.8 eeee) eee eeeeeee ee −88 ee −88°M eee 88 eee, eee eeee 8 M MMe (88 eM) eee eeeee. Meeee eeeeeeee eeeeeee eeeeee eee eeeeeeeeee eeee eeeeeee, eeeeeeee ee eeeeee eeeeeeeeeeeeeee eeeeeeeeeeee, eee eeeeeee eee eeeeeeee ee eeeeeeeee eeeeeeee; eeeee: 88 ee (88%).

8,8,8-Meee[(8-eeee-eeeee-8,8-eeeeeeeeeeeeeee)eeeeeee]eeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee MMM, eeeeeee eeeeeeee eeee eMe8MM (8.88 e, 8.8 eeee) eee 8.8 M MeMe ee eeeeee (8.88 eM, 8.8 eeee), ee MMM (88 eM) eee eeeee ee eee eeeeeee(eeeeeeeeeeee) eeeeeeeeee ‌88‌ (8.8 e, 8.88 eeee) ee eee MMM (88 eM) ee −88°M. Meeee 88 eee, eee eeeeeeee eee eeeeeeee eeee eee. MM8Me eeee eee eeeeee ee ee. Mee eeeeeee eee eeeeeeeee eeee MM8Me8 eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee e eeeeee eeeeeeeeee. Meeeeeeeeeeeeee eeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeeee 8:8) ee eee eeeee eeeeeee eeee e eeeeeeeee eeeee; eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8e, 888.