α,β-不飽和イミンへの共役付加反応を用いる新規合成反応

概要

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The development of a new efficient synthetic method of nitrogen containing compounds is extensively studied because there are many nitrogen containing compounds such as amino acids, alkaloids, and β-lactams having biological activities and functionalized materials for organic electronics or photonics. During the investigation of Mannich-type reactions of α,β-unsaturated imines with ketene silyl acetals, we found that 1,4-and 1,2-double nucleophilic addition reactions proceeded to give doubly alkylated products in good yields. Various nucleophiles can be also used such as allyltins, ketene silyl thio acetals, trimethylsilyl cyanide, thiols, and hydrogen azide. Using 1,4-and 1,2-double nucleophilic addition reactions with ketene silyl acetal and trimethylsilyl cyanide as a key reaction, an imidazole glycerol phosphate dehydratase inhibitor(IGPDI) possessing a monopyrrole aldehyde moiety is synthesized. 2-Iminopyridine synthesis is found in the conjugate addition of cyanoacetate derivatives to alkynyl imines. Stereodivergent synthesis of both cis-and trans-β-lactams is presented using the following three reactions: Iminocyclobutenone formation, chemoselective reduction of imino groups, and thermal rearrangement of aminocyclobutenones as crucial steps, in which the starting materials, iminocyclobutenones, were readily synthesized using conjugate addition reactions of alkynyl imines with ketene silyl acetals in good yields.
2010-10-01