A multistep single-crystal-to-single-crystal bromodiacetylene dimerization

Tobias N. Hoheisel, Stephen Schrettl, Roman Marty, Tanya K. Todorova, Clémence Corminboeuf, Andrzej Sienkiewicz, Rosario Scopelliti, W. Bernd Schweizer, Holger Frauenrath

Research output: Contribution to journalArticlepeer-review

41 Scopus citations

Abstract

Packing constraints and precise placement of functional groups are the reason that organic molecules in the crystalline state often display unusual physical or chemical properties not observed in solution. Here we report a single-crystal-to-single-crystal dimerization of a bromodiacetylene that involves unusually large atom displacements as well as the cleavage and formation of several bonds. Density functional theory computations support a mechanism in which the dimerization is initiated by a [2 + 1] photocycloaddition favoured by the nature of carbon-carbon short contacts in the crystal structure. The reaction proceeded up to the theoretical degree of conversion without loss of crystallinity, and it was also performed on a preparative scale with good yield. Moreover, it represents the first synthetic pathway to (E)-1,2-dibromo-1,2-diethynylethenes, which could serve as synthetic intermediates for the preparation of molecular carbon scaffolds. Our findings both extend the scope of single-crystal-to-single-crystal reactions and highlight their potential as a synthetic tool for complex transformations.

Original languageEnglish
Pages (from-to)327-334
Number of pages8
JournalNature Chemistry
Volume5
Issue number4
DOIs
StatePublished - Apr 2013
Externally publishedYes

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