(2R,3R)-3-[(1R)-1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl]-4-oxoazetidin-2-yl Acetate in Zinc- and Samarium-Promoted Substitution Reactions with Methyl 2-Bromopropanoate and Methyl (2-Bromomethyl)prop-2-enoate. Unusual Cleavage of the N1‒C4 Bond in Azetidin-2-one Derivative with Migration of Methoxycarbonyl Group in Synthetic Approaches to Carbapenems and Their Analogs


Дәйексөз келтіру

Толық мәтін

Ашық рұқсат Ашық рұқсат
Рұқсат жабық Рұқсат берілді
Рұқсат жабық Тек жазылушылар үшін

Аннотация

The use of zinc in Barbier-type reactions of (2R,3R)-3-[(1R)-1-{[tert-butyl(dimethyl)silyl]oxy}-ethyl]-4-oxoazetidin-2-yl acetates with halogen derivatives led to the formation of expected substitution products. The reaction of the title compound with a reagent prepared from samarium powder, a catalytic amount of iodine, and methyl 2-bromopropanoate in THF gave an anomalous substitution product, methyl 2-{(2S,3S)-3-[(1R)-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl]-4-oxoazetidin-2-yl}-2(R,S)-methyl-3-oxopentanoate. Alkylation of the latter with methyl bromoacetate afforded methyl 2-{(2S,3S)-3-[(1R)-1-{[tert-butyl(dimethyl) silyl]oxy}ethyl]-1-(2-methoxy-2-oxoethyl)-4-oxoazetidin-2-yl}-2(RS)-methyl-3-oxopentanoate which underwent fragmentation through cleavage of the N1–C4 bond under the action of sodium bis(trimethylsilyl)-amide in THF at–78°C. The resulting acyclic amide, dimethyl {(2R,S,3Z)-2-[(1R)-1-{[tert-butyl(dimethyl)-silyl]oxy}ethyl)]-4-methyl-5-oxohept-3-enoylamino}malonate, was smoothly converted to new functionalized N-substituted pyrrolidinones via intramolecular Michael type cyclization in methylene chloride in the presence of NEt3–DMAP–Boc2O.

Авторлар туралы

Z. Valiullina

Institute of Organic Chemistry, Ufa Research Center

Email: bioreg@anrb.ru
Ресей, pr. Oktyabrya 71, Ufa Bashkortostan, 450054

L. Khasanova

Institute of Organic Chemistry, Ufa Research Center

Email: bioreg@anrb.ru
Ресей, pr. Oktyabrya 71, Ufa Bashkortostan, 450054

N. Selezneva

Institute of Organic Chemistry, Ufa Research Center

Email: bioreg@anrb.ru
Ресей, pr. Oktyabrya 71, Ufa Bashkortostan, 450054

L. Spirikhin

Institute of Organic Chemistry, Ufa Research Center

Email: bioreg@anrb.ru
Ресей, pr. Oktyabrya 71, Ufa Bashkortostan, 450054

Yu. Belokon’

Nesmeyanov Institute of Organoelement Compounds

Email: bioreg@anrb.ru
Ресей, ul. Vavilova 28, Moscow, 119991

M. Miftakhov

Institute of Organic Chemistry, Ufa Research Center

Хат алмасуға жауапты Автор.
Email: bioreg@anrb.ru
Ресей, pr. Oktyabrya 71, Ufa Bashkortostan, 450054

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