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Synthesis of chiral 1,4-oxazepane-5-carboxylic acids from polymer-supported homoserine.

ABSTRACT: The preparation of novel 1,4-oxazepane-5-carboxylic acids bearing two stereocenters is reported in this article. Fmoc-HSe(TBDMS)-OH immobilized on Wang resin was reacted with different nitrobenzenesulfonyl chlorides and alkylated with 2-bromoacetophenones to yield N-phenacyl nitrobenzenesulfonamides. Their cleavage from the polymer support using trifluoroacetic acid (TFA) led to the removal of the silyl protective group followed by spontaneous lactonization. In contrast, TFA/triethylsilane (Et₃SiH)-mediated cleavage yielded 1,4-oxazepane derivatives as a mixture of inseparable diastereomers. The regioselectivity/stereoselectivity depended on the substitution of the starting 2-bromoacetophenones and was studied in detail. Catalytic hydrogenation of the nitro group improved the separability of the resulting diastereomeric anilines, which allowed us to isolate and fully characterize the major isomers.

SUBMITTER: Kralova P

PROVIDER: S-EPMC9056997 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Synthesis of chiral 1,4-oxazepane-5-carboxylic acids from polymer-supported homoserine.

Králová Petra P Lemrová Barbora B Maloň Michal M Soural Miroslav M

RSC advances 20200930 59

The preparation of novel 1,4-oxazepane-5-carboxylic acids bearing two stereocenters is reported in this article. Fmoc-HSe(TBDMS)-OH immobilized on Wang resin was reacted with different nitrobenzenesulfonyl chlorides and alkylated with 2-bromoacetophenones to yield <i>N</i>-phenacyl nitrobenzenesulfonamides. Their cleavage from the polymer support using trifluoroacetic acid (TFA) led to the removal of the silyl protective group followed by spontaneous lactonization. In contrast, TFA/triethylsilan ...[more]

PMID: 35517075

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