Synthesis, Table of Contents Synthesis 2018; 50(23): 4606-4610DOI: 10.1055/s-0037-1610659 psp © Georg Thieme Verlag Stuttgart · New YorkPreparation of Rearranged Allylic Isocyanates from the Reaction of Allylic Alcohols with 1-Cyano-4-dimethylaminopyridinium Bromide Authors Author Affiliations Daler Baidilov Mariia Makarova Lukas Rycek Tomas Hudlicky * Department of Chemistry and Centre for Biotechnology, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, Canada Email: thudlicky@brocku.ca Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract A shorter and less costly alternative to Ichikawa’s [1,3]-transposition protocol for cyanates to isocyanates is described. Key words Key wordssigmatropic rearrangement - [1,3]-transposition - allylic alcohol - methodology - total synthesis Full Text References References 1a Christophersen C. Holms A. Acta Chem. Scand. 1970; 24: 1512 For the related [3,3]-sigmatropic rearrangement of allylic thiocyanates see: 1b Smith PA. Emerson DW. J. Am. Chem. Soc. 1960; 82: 3076 For other examples of [3,3]-sigmatropic rearrangements see: 1c Ramadhar TR. Kawakami J. Batey RA. Synlett 2017; 28: 2865 1d Ramb DC. Kost L. Haufe G. Chimia 2014; 68: 436 1e Mingat G. MacLellan P. Laars M. Clayden J. Org. Lett. 2014; 16: 1252 2 Overman LE. Kakimoto M. J. Org. Chem. 1978; 43: 4563 For the discovery of this reaction, see: 3a Ichikawa Y. Synlett 1991; 238 For recent reviews in this field, see: 3b Ichikawa Y. Synlett 2007; 2927 3c Mailyan AK. Eickhoff JA. Minakova AS. Gu Z. Lu P. Zakarian A. Chem. Rev. 2016; 116: 4441 For the detailed experimental procedure, see: 3d Ichikawa Y. Kariya N. Hasegawa T. Org. Synth. 2013; 90: 271 For the stereochemistry of the reaction, see: 3e Ichikawa Y. Tsoboi K. Isobe M. J. Chem. Soc., Perkin Trans. 1 1994; 2791 4a Whitten JP. Mcarthy JR. Matthews DP. Synthesis 1988; 470 4b Waselman M. Guibe-Jampel E. Raoult A. Busse WD. J. Chem. Soc., Chem. Commun. 1976; 21 5 Enehydroxylamines react with CAP to afford imidazolidinones in a similar 3,3-sigmatropic rearrangement reaction: Reis LV. Lobo AM. Prabhakar S. Duarte MP. Eur. J. Org. Chem. 2003; 190 6 Wilson R. Bedard K. Baidilov D. Tius M. Hudlicky T. Tetrahedron Lett. 2018; 59: 2467 7 Okamoto R. Tanaka K. Org. Lett. 2013; 15: 2112 8 Szcześniak P. Pieczykolan M. Stecko S. J. Org. Chem. 2016; 81: 1057 9 Mainetti E. Fresterbank L. Malacria M. Synlett 2002; 923 10 Valeev RF. Khasanova LS. Miftakhov MS. Russ. J. Org. Chem. 2010; 46: 670 11a Maehara T. Motoyama K. Toma T. Yokoshima S. Fukuyama T. Angew. Chem. Int. Ed. 2017; 56: 1549; Angew. Chem. 2017, 129, 1571 11b Baidilov D. Rycek L. Trant JF. Froese J. Murphy B. Hudlicky T. Angew. Chem. Int. Ed. 2018; 57: 10994; Angew. Chem. 2018, 130, 11160 Supplementary Material Supplementary Material Supporting Information (PDF) (opens in new window)
