0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content. Method 6: Mitsunobu Lactonization

DOI: 10.1055/sos-SD-020-01369

Maier, M. E.Science of Synthesis, (2007201475.

In the Mitsunobu reaction the adduct of triphenylphosphine and dialkyl azodicarboxylate causes activation of a hydroxy function via formation of an oxophosphonium intermediate 182 (Scheme 81). The activated hydroxy group can then be substituted with nucleophiles such as carboxylates.[‌247‌] With hydroxy acids 181, lactones 183 can be obtained. Some mechanistic studies have been reported.[‌248‌‌255‌]

Meeeee 88 Meeeeeeee ee Meeeeee Meeeeeeee ee eee Meeeeeeee Meeeeeee[‌888‌]

Meeeee eeeeeeeeeee eeeeeee eeeeeee eeee eeeeeeeee eee eeeeeeeeeeeeeeeeee eeeeee ee eeeeeeeeeee ee eee eeeeeee eeeeeeee eee eeee eeeee ee eee eeeeeee.[‌888‌,‌888‌] Me eee eeeeeeeeeeeee ee eee 8-eeeeeee eeee 888, eeeeee eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeeeee eeeeeee ee eeeeeeee (Meeeee 88). Meee ee ee eeeeeeeeee eeee eee eeeeeee 888, eeeee eee eeeeeeeeeee eeeeeee eee eeeeeeeeeeeeeeeee eeee. Me eeeeeeee, eee eeee eeeeeeeeee eeeeeee ee eee eeee eeeeeeee 8-eeeeeee eeee 888 eeeeeeee eeeeeee 888 eeee eeeeeeeee ee eeeeeeeeeeeee. Meee eeeeee eee ee eeeeeeeeee ee eeeeee ee eee eeeeeeee ee eee eeeeeeeeeeeeeeeeee eeeee. Meee, ee eeeee eeee eeeee ee e eeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeeeeeeeee eeee eee eee eeeeeeeeeeeeeeeee eeee.

Meeeee 88 Meeeeeee eeee Meeeeeeee eee Meeeeeeee ee Meeeeeeeeeeee ee eee Meeeeeeee Meeeeeeeeeeee[‌888‌,‌888‌]

β-Meeeeeee eee ee eeeeeeee eeee eeeeeeee-eeeeeeeee eeeeeee eeeee Meeeeeeee eeeeeeeeee ee eee eeeeeeeeeeee (Meeeee 88). Meee, eeeeeeee 888[‌888‌] eee 888[‌888‌] eee eeeeeeee ee eeee eeeeee. Meeee eeeeeeee eee eeeeeeeeeee eeeeeeee eeeeee eeeee eeee eeeee eee eeeeeeeeeeee eeeeeee. Meeeeee, e eeeeeeeeeee ee eee 8-eeeeeeee eeeeee eeeeeeeeeee, eeeeeeeee ee eeeeeeee eeee ee 888.[‌888‌]

Meeeee 88 β-Meeeeeee ee eee Meeeeeeee Meeeeeee[‌888‌,‌888‌,‌888‌]

Meeee eeeeee eeee eeeeeeee eeeeeee eeeee eeeeee, eee Meeeeeeee eeeeeeeeeeeee ee eeee eeeeeeeeeee ee, eee eeeeee eeeeeee, eeeeeeeee ee eee eeeeeee-eeeeeee eeeeeeeeeeee ee eeeeeeeee. Meee, eeeeeee eeeeeeeee ee eeeeeee eeeeeeee eee ee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeee eeeee, e.e. 888,[‌888‌] 888,[‌888‌] 888,[‌888‌] eee 888[‌888‌] (Meeeee 88).

Meeeee 88 Meeeee Meee Meeeeeee ee eee Meeeeeeee Meeeeeee[‌888‌‌888‌]

Mee eeeeeeeeeeeee ee eee eeeeeeeee eeee 888 eeeeeeeeeee eee eeeeeeeeeeeeeee ee eee eee eeeeeee eeeeeeeee ee eeeeeee eeeeeeeee (Meeeee 88). Me eeeeeeee, eeeeeeeeeee ee eeeeeee eeee 888 eeeee eeeee eeee eeeeeeeee ee eeeeeeeeeeeee, eeeeeeeee eeeeeee 888.[‌888‌]

Meeeee 88 Meeeeeeee Meeeeeeeeeeee ee e Meeee ee Meeeeeeeeeeee Mee Meeeeee Meeeeeeee[‌888‌]

Mee Meeeeeeee eeeeeeeeeeeee eee eeee eeeeee eee eeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeeee. Meeeeeeeee, ee ee eeee eeeeeeeeee ee eeeeeee e eeeeeeeeeee eeeeeeeee eeeee eeeeeeee eeeeeeeee eeeeee eee eeeeeeeeeeeee eeee (Meeee 88).[‌888‌‌888‌] Mee eeeeeee 888 eeeee eeee eee Meeeeeeee eeeeeeeeee eee eeee eeee eee ω-eeeeeee eeeee eeee eeeeeee eeeeeee eeeeeeee.

Meeee 88 Meeeeeeeeeeeeeeeee eee eee Meeeeeeee Meeeee[‌888‌‌888‌]

Meeeeee Meeeeeeeee Meeee (%) Mee
Me8M, MMMM, eeeeeee 88 [‌888‌,‌888‌]
Me8M, MMMM, eeeeeee 88 [‌888‌]
Me8M, MMMM, eeeeeee 88e [‌888‌]
Me8M, MMMM,e MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee 88 [‌888‌]
Me8M, MMMM, MMM 88 [‌888‌]

e Meee=8-(eeeeeeeeeeeeee)eeeeeeeeeeeeee.

e MMMM=eeeeeeeeeee eeeeeeeeeeeeeeee.

Mee eeeeeeee ee Meeee 88, eeeee eeeeeee e eeeeee eeeee eeeeee, eee eeeeeeee eeee eee eeeeeeeeeeeee ω-eeeeeee eeeee ee eeeeeeeeeeeeeeeeee eeeee Meeeeeeee eeeeeeeeee.[‌888‌‌888‌] Me eee eeee ee 888, eeeeeee eeeeeeeeeeeee eeeeeee eeee eeee ee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee.

Meeee 88 Meeeeeeee ee Meeeee Meeee Meeeeeee[‌888‌‌888‌]

Meeeeee Meeeeeeeee Meeee (%) Mee
Me8M, MMMM, eeeeeee 88 [‌888‌]
Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee 88 [‌888‌]

Meeeeee eee ee-eeeeeee eeee eeeeeeeee eeeeeee-eeeeeeeee eeeee eeeeeeeeeeeeeeeee (Meeeee 88).[‌888‌] Meeee eee eeeeeeee eeee eeeeeeeeeeeee eeeeeeeeeee (8% eeeee eeeeee), eeeeeeee, eeeeee eeeeeeeeee, eee e eeeee eeeeeeeee. Me eee eeeee eeeeeeee, eee eeeeee eeee eeeee- eee eeeeeeeeeeeeee eeeeeee eeeeeeeeeeeee eee eeeeeeeeee. Meeeeeeeeee, eeeeeee eeeeeeeee ee eeeeeeeeeee. Meeee eeeee, eee eeeeeeeee eeeeeee eee ee eeeeeeeeee eee eeeeee.

Meeeee 88 Meeeeee-Meeeeeeee Meeee Meeeeeeeeeeeeeeee[‌888‌]

Mee Meeeeeeee eeeeeeeeeeeeeeeeee ee e eeeeeeee eeeeee ee eee eeeeeeeee ee eeeeeeeeeeeee. Meeee eeeeeeeeee eeeeeeeee eee eeeeeeeeee eeeeeeee eeeeee eee eeeeeeeeee eeeeeeee eee eeeeeee eeeeeeeeeeeee eeeeeee eee ee eeeeeeeeee. Me eeeeeee, 88- ee 88-eeeeeeee eeeeeeee eee eeeeeeee (Meeee 88).[‌888‌‌888‌] Me eee eeeeeeeeeeeeeeeeee ee eee eeeeeee 888 eee eee ee eeeeeeeeeee eeeeeeeeeeeeeeeeee eeeeee ee ee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeeee ee eeeeeeee. Meeeeee eeee-eeeeeeee eeeeeeeeee (8.888M ee eeeeeeeeeeeeeee) eeee eeee ee eeee 88% ee 888, eee eeeee eeee eeeeeeeeeee eeeeeeeeeeeeeeeeee eeeeeeeee ee 88%. Me eeee eeee, eee eeeeeeee eee ee eee ee e eeeeee eeeeeeeeeeeee (8.88M).[‌888‌]

Meeee 88 Meeeeeeeeeeee eee Meeeeeeee Meeeeeeeeeeee[‌888‌‌888‌]

Meeeeee Meeeeeeeee Meeee (%) Mee
eeeee-Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee 88 [‌888‌]
Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee 88 [‌888‌]
Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]
Me8M, MMMM, eeeeeee/MMM 88 [‌888‌]