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. 2018 May 18;83(10):5650-5664.
doi: 10.1021/acs.joc.8b00640. Epub 2018 May 2.

Desymmetrization of Cyclopropenes via the Potassium-Templated Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial Activity

Vladimir A Maslivetc  1 , Danielle N Turner  2 , Kimberly N McNair  2 , Liliya Frolova  2 , Snezna Rogelj  2 , Anna A Maslivetc  1 , Nicolai A Aksenov  3 , Marina Rubina  1 , Michael Rubin  1   3
Affiliations

Desymmetrization of Cyclopropenes via the Potassium-Templated Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial Activity

Vladimir A Maslivetc et al. J Org Chem. .

Abstract

A strain-release-driven, cation-templated intramolecular nucleophilic addition of tethered alkoxides to prochiral cyclopropenes is described. Employment of chiral β- and γ-amino alkoxides allowed for highly diastereoselective assembly of a small series of enantiopure cyclopropane-fused oxazepanones. It was shown that the chiral center at C-4 plays a crucial role in controlling desymmetrization of the cyclopropenyl moiety, instigated by a profound potassium-templated effect. The preliminary biological activities of the new cyclopropane-fused medium heterocycles against Gram-positive bacteria, Gram-negative bacteria, mycobacteria, cancer cells, and fungus were evaluated.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Structures and yields of racemic cyclization products 17. Yields of purified materials are provided.
Figure 2.
Figure 2.
Structures and yields of enantiopure cyclization products 19. Yields of purified materials are provided.
Figure 3.
Figure 3.
Structures and yields of chiral cyclization products 25 and 28. Yields of purified materials are provided.
Scheme 1
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Scheme 11
See this image and copyright information in PMC

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