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Austin, D. J.; Miller, S. M., Science of Synthesis, (2005) 21, 104.
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]
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
[50] | Meeeeeeee, M.; Meeeeeee, M.; Meeeee, M., Meee. Meee., (8888), 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 8-8, 8888.