Orbital-Overlap Control in the Solid-State Reactivity of β-Azido-Propiophenones:  Selective Formation of cis-Azo-Dimers

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Abstract

Solid-state photolysis of 1a,b yields selectively cis-3a,b. X-ray analysis of 1a,b reveals the molecules adopt an extended structure and as such the crystal packing arrangement consists of planar, π-stacked molecules. The shortest intermolecular distance between adjacent N-atoms is 3.76 Å and would lead to formation of trans-3a,b, whereas cis-3a,b is formed by dimerization between N-atoms that are 3.9 Å apart. We propose that the molecular orbital alignment of the adjacent nitrenes controls the solid-state reactivity.

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This article has been cited by 6 ACS Journal articles (5 most recent appear below).

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    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Synthesis of Azines in Solid State: Reactivity of Solid Hydrazine with Aldehydes and Ketones

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    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Triplet-Sensitized Photoreactivity of a Geminal Diazidoalkane

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    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Controllable Selective Functionalization of a Cavitand via Solid State Photolysis of an Encapsulated Phenyl Azide

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    Organic Letters2009 11 (14), 3056-3058

    Phenyl azide (1) has been encapsulated within cavitand 2 to form a 1:1 complex of 1@2 in the solid state. Subsequent irradiation affords two diastereomeric nitrene addition products 5 and 7. The ratio of 5 and 7 can be reversed by thermally induced ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Intramolecular H-Atom Abstraction in γ-Azido-Butyrophenones: Formation of 1,5 Ketyl Iminyl Radicals

  Sivaramakrishnan Muthukrishnan, Jagadis Sankaranarayanan, Rodney F. Klima, Tamara C. S. Pace, Cornelia Bohne and Anna D. Gudmundsdottir
  Organic Letters2009 11 (11), 2345-2348

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    Organic Letters2009 11 (11), 2345-2348

    Photolysis of γ-azidobutyrophenone derivatives yields 1,4 ketyl biradicals via intramolecular H-atom abstraction. The 1,4 ketyl biradicals expel a nitrogen molecule to form 1,5 ketyl iminyl biradicals, which decay by ring closure to form a new carbon−...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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