Mn(III)-mediated reactions of cyclopropanols with vinyl azides: synthesis of pyridine and 2-azabicyclo[3.3.1]non-2-en-1-ol derivatives.
A Mn(III)-mediated divergent synthesis of substituted pyridines and 2-azabicyclo[3.3.1]non-2-en-1-ol derivatives was exploited using readily available vinyl azides and cyclopropanols with a wide range of substituents. In short, the reactions of vinyl azides with monocyclic cyclopropanol provided pyridines in the presence of Mn(acac)(3) (1.7 equiv), whereas those with bicyclic cyclopropanols led to the formation of 2-azabicyclo[3.3.1]non-2-en-1-ol derivatives using a catalytic amount of Mn(acac)(3). These reactions may be initiated by a radical addition of beta-keto radicals, generated by the one-electron oxidation of cyclopropanols, to vinyl azides to give iminyl radicals, which would cyclize with the intramolecular carbonyl groups. In addition, versatile transformations of 2-azabicyclo[3.3.1]non-2-en-1-ol to 2-azabicyclo[3.3.1]nonane or -non-2-nen frameworks were developed.
Wang
Yi-Feng
YF
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Chiba
Shunsuke
S
D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004988:Ethers, Cyclic / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D011725:Pyridines / Q000138:chemical synthesis*
D001372:Aza Compounds; D001386:Azides; D001643:Bridged Bicyclo Compounds; D004988:Ethers, Cyclic; D011725:Pyridines; C043657:cyclopropanol; D008345:Manganese; C023666:pyridine