New synthetic reactions. Alkylation of lactam derivatives

Five-, Six-, and Seven-membered Lactim Ethers. Methods of Synthesis and Chemical Properties. (Review)

“…In the case of the least reactive β-phenylethyl bromide the yields of compounds 99 and 100 were 27 and 12% (100°C, 28 h [3,129] The action of lithium diisopropylamide (LDA) on the lactim ether from valero-or caprolactam leads to isomerization of the double bond in the lactim ether with the formation of compounds 101. The latter react with the halogen derivatives 102 and are converted into the lactim ether 103 [23,130]. Compounds 106 or 107 were synthesized with yields of 43-63% from the salts 96 and the bromides 104 or 105 by the Reformatsky reaction by heating in sealed tubes [131].…”

“…At room temperature butyrolactim methyl ether and the triflate 208 form the salt 209, which is converted into 1-(trimethylsilylmethyl)butyrolactone 210 when treated with 1,4-diazabicyclo[2.2.2]octane (DABCO) [197]. The addition product 213 was obtained with a yield of 31% as a result of reaction of the lithium derivative of the lactim ether 101 (n = 2) with methyl vinyl ketone [130]. The sulfide 214 (yield 66%) was synthesized from the same derivative 101 and diphenyl disulphide under analogous conditions [130].…”

“…The addition product 213 was obtained with a yield of 31% as a result of reaction of the lithium derivative of the lactim ether 101 (n = 2) with methyl vinyl ketone [130]. The sulfide 214 (yield 66%) was synthesized from the same derivative 101 and diphenyl disulphide under analogous conditions [130].…”

Milieux hyperbasiques: préparation et alkylation de carbanions en α d'amides N,N-disubstitués. Application à la synthèse de la d,l-pipéritone

“…Le rendement est de 82y0 alors qu'il n'est que de 45y0 lorsqu'on emploie l'amidure de sodium dans l'ammoniac liquide (3). Des publications rCcentes dkcrivent des synthbes analogues en traitant la N-mCthyl pipCridone-2 par les dialkylainidures usuels, mais la rCaction nkcessite l'emploi de dCrivCs halogCnCs trks rCactifs (14). La riduction des ainides conduit rapidenlent aux aldChydes, alcools ou anlines mais nous nous somines plus particulierement attach& B la priparation de cCtones alkylkes rCgiosClectivement.…”

An Aza-Enolate Alkylation Strategy for the Synthesis of α-Alkyl-δ-amino Esters and α-Alkyl Valerolactams

“…6 Lactim ether bonds are easily hydrolysed using mild aqueous acid, 7 and as a consequence we reasoned that hydrolysis of a-alkyl lactim ethers 5 would also afford a route to their corresponding a-alkyl-d-amino methyl ester hydrochloride salts 6. Subsequent neutralisation of these hydrochloride salts with base would then result in intramolecular cyclisation to give their corresponding a-alkyl lactams 7 (Scheme 2).…”