Navigation

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.
21.1.3.14 Method 14: Reaction of Acetals with Isocyanides

DOI: 10.1055/sos-SD-021-00059

Austin, D. J.; Miller, S. M.Science of Synthesis, (200521104.

Isocyanides react with acetals in the presence of titanium(IV) chloride to provide imidoyl chlorides 68, which can be hydrolyzed directly to the corresponding α-alkoxylated amides 69 in good yields. In order to form the imidoyl chloride it seems likely that an active titanium acetal complex is formed initially and this is then attacked at the highly electrophilic carbon site by the carbon terminus of the isocyanide (Scheme 33). The reaction occurs at low temperature but it is unsuitable for substrates that are reactive to strongly Lewis acidic conditions.[‌50‌]

Meeeee 88 Meeeeeeee ee α-Meeeeeeeeee Meeeee eeee Meeeeeeeeee eee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeeeeee Meeeeeeeeee (°M) Meee (e) Meeee (%) ee 88 Mee
Me M Me Me 88 8 88 [‌88‌]
Me M Me (MM8)8Me 88 ee 88 8 88 [‌88‌]
(MM8)8Me M Me (MM8)8Me 88 ee 88 8 88 [‌88‌]
Me M Me (MM8)8Me 88 ee 88 8 88 [‌88‌]
MM=MMMee M Me (MM8)8Me 88 ee 88 8.8 88 [‌88‌]
MM=MMMee M Me (MM8)8Me 88 ee 88 8 88 [‌88‌]
(MM8)8Me Me Me (MM8)8Me 88 ee 88 8 88 [‌88‌]
(MM8)8Me M Me 8,8-Me8M8M8 88 ee 88 8 88 [‌88‌]

e M-Meeeee.

Meeeeeeeeeee Meeeeeeee

M-Meeeeeeeee-α-eeeeeeeeeeeeeeeeeeeeee (88, M8 = Me; M8 = M; M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

MeMe8 (8.8 eeee) ee MM8Me8 (8.8 eM) eee eeeee ee e eeeeeee eeee ee MM8Me8 (8 eM), eeeeeeeeee eeeeeeeeee (8 eeee) eee eeeeeeeeeeee eeeeeeee eeeeee (8 eeee) eeeeeeeeee ee 88°M eeeee eeeee. Mee eeeeeee eee eeeeeee ee eeee eeeeeeeeeee eee 8 e eee eeee eee. ee MeMMM8 eee eeeee. Meeee e eeeeee eeeeee, eee eeeee eeeeeeee eee eeeeeeee; eeeee: 88%.

References