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

Miran Lemmerer; Michael Abraham; Bogdan R Brutiu; Alexander Roller; Michael Widhalm

doi:10.3390/molecules24173098

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

Molecules. 2019 Aug 26;24(17):3098. doi: 10.3390/molecules24173098.

Authors

Miran Lemmerer¹, Michael Abraham², Bogdan R Brutiu¹, Alexander Roller³, Michael Widhalm⁴

Affiliations

¹ Institute of Organic Chemistry, University of Vienna, Währinger Straße 38, 1090 Wien, Austria.
² Institute of Chemical Catalysis, University of Vienna, Währinger Straße 38, 1090 Wien, Austria.
³ Institute of Inorganic Chemistry, University of Vienna, Währinger Straße 42, 1090 Wien, Austria.
⁴ Institute of Chemical Catalysis, University of Vienna, Währinger Straße 38, 1090 Wien, Austria. m.widhalm@univie.ac.at.

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.

Keywords: 2,2′-diamino-1,1′-binaphthyl; diaza-macrocycle; dihydroxylation; epoxidation; heterocycle; rearrangement; ring closing metathesis; ring contraction.

MeSH terms

Crystallography, X-Ray
Cyclization
Epoxy Compounds / chemical synthesis*
Epoxy Compounds / chemistry
Models, Molecular
Molecular Structure
Naphthalenes / chemistry*
Stereoisomerism

Substances

Epoxy Compounds
Naphthalenes
1,1'-binaphthyl