Development of new synthetic methods utilizing reactivity of alkylidenecarbenes

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1. N-Tosyl-o-acylanilines smoothly reacted with lithium salt of trimethylsilyldiazomethane (TMSCHN_2) to give 3-substituted indoles via an alkylidenecarbene intermediate in good yield.2. The copper (II)-catalyzed cross-coupling of 3-trimethylsilylindazoles with arylboronic acids regioselectively gave the corresponding 1-aryl-3-trimethylsilylindazoles in high yields.3. Reaction of TMSCHN_2, acylisocyanates, and N-phenylmalenimide gave bicyclic 2-pyridones in good yields in a one-pot process.4. Aryloxypyruvates reacted with TMSC(Ll)N_2 to give 1,2-dihydro-1-oxaazulene-3-carboxylates via an alkylidenecarbene intermediate in moderate yields.5. o-Acyl-N-pivaloylanilines smoothly reacted with TMSC(Li)N_2 to give o-alkynyl-N-pivaloylanilines via an alkylidenecarbene intermediate in good yield.6. Reaction of N-Tosyl-o-acylanilines with TMSC(Li)N_2, followed by treatment with t-BuLi and then electrophiles gave 2,3-disubstituted N-tosylindoles in a one-pot process.7. Reaction of -αketoesters with magnesium bromide salt of TMSCHN_2 followed by in situ treatment with pivalic acid gave a-substituted β-trimethylsilyl-α,β-epoxyesters in an efficient and cis-selective manner.