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Russian Chemical Bulletin

, Volume 63, Issue 11, pp 2502–2508 | Cite as

Synthesis of 11-methyl-13-azabicyclo[7.3.1]trideca-3,10-diene, a macrobicycle with the 9b-azaphenalene carbon framework, based on the combination of allylboration and intramolecular metathesis

  • N. Yu. Kuznetsov
  • V. N. Khrustalev
  • T. V. Strelkova
  • Yu. N. Bubnov
Full Articles

Abstract

A four-step synthesis of 11-methyl-13-azabicyclo[7.3.1]trideca-3,10-diene, a potential precursor of the ladybugs´ defensive alkaloids precoccinelline and mirrhine, has been accom-plished. Treatment of 4-picoline with 5-hexenyl-1-lithium, triallylborane, and methanol led to the synthesis of trans-6-allyl-2-(hex-5-enyl)-4-methyl-1,2,3,6-tetrahydropyridine, which reacted with triallylborane upon heating to be converted to the cis-isomer. A subsequent cyclization of the cis-isomer of N-Boc derivative via the intramolecular metathesis using Grubbs II and Hoveyda—Grubbs II ruthenium catalysts furnished the target bridged macrobicycle. The structure of its hydrochloride was confirmed by single crystal X-ray diffraction studies. The optimal conditions for the metathesis reaction and the isolation of the macrobicyclic product were selected.

Keywords

mirrhine precoccinelline allylboranes allylboration bridged azabicycles macrocyclization metathesis 

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Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation
  2. 2.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation

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