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Synthesis, Structure, and Reactivity of Binaphthyl Supported Dihydro[1,6]diazecines.

ABSTRACT: A short approach to chiral diaza-olefines from protected 2,2'-diamino-1,1'-binaphthyl is presented. Cis- and trans-olefines can be selectively obtained by twofold N-allylation followed by RCM or by bridging a 2,2'-diamino-1,1'-binaphthyl precursor with trans-1,4-dibromo-2-butene. Deprotection afforded cis- and trans-dihydro[1,6]diazecines 1 in 58 and 64% overall yield. The reactivity of the but-2-ene-1,4-diyl fragment was investigated yielding corresponding epoxides, diols, and mono- and dibromo products. In several cases rearrangements and participation of the proximate N-Boc group was observed. In no case could allylic substitution be accomplished. From 13 compounds X-ray structure analyses could be obtained.

SUBMITTER: Lemmerer M

PROVIDER: S-EPMC6749229 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Synthesis, Structure, and Reactivity of Binaphthyl Supported Dihydro[1,6]diazecines.

Lemmerer Miran M Abraham Michael M Brutiu Bogdan R BR Roller Alexander A Widhalm Michael M

Molecules (Basel, Switzerland) 20190826 17

A short approach to chiral diaza-olefines from protected 2,2'-diamino-1,1'-binaphthyl is presented. Cis- and trans-olefines can be selectively obtained by twofold N-allylation followed by RCM or by bridging a 2,2'-diamino-1,1'-binaphthyl precursor with trans-1,4-dibromo-2-butene. Deprotection afforded cis- and trans-dihydro[1,6]diazecines 1 in 58 and 64% overall yield. The reactivity of the but-2-ene-1,4-diyl fragment was investigated yielding cor ...[more]

PMID: 31455006

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