Tiffeneau–Demjanov Rearrangement by Using α-Chloro-α-diazoacetate: A Direct Access to α-Chlorinated Medium-Size-Ring Ketones via Ring Enlargement

Abstract

α-Chloro(diazo)acetate can be readily used in an intermolecular ring expansion catalyzed by a boron Lewis acid to construct α-chlorinated medium-size cyclic ketones. This intermolecular Tiffeneau–Demjanov reaction proceeds in good yield from easily prepared or commercially available starting materials and allows the concomitant formation of a tetrasubstituted stereocenter.

Key words

tetrasubstituted stereocenter - α-halogenation - ring expansion - chloro(diazo)acetate - cyclic ketones

• References

• 1a Butler A, Carter-Franklin JN. Nat. Prod. Rep. 2004; 21: 180
• 1b Murphy CD. J. Appl. Microbiol. 2003; 94: 539
• 2 Gribble GW. J. Chem. Educ. 2004; 81: 1441
• 3a De Kimpe N, Verhe R. The Chemistry of α-Haloketones, α-Haloaldehydes and α-Haloimines. John Wiley & Sons; New York: 1988
• 3b Ramachandran PV. Asymmetric Fluoroorganic Chemistry: Synthesis, Applications, and Future Directions. ACS Symposium Series 746, American Chemical Society; Washington DC: 2000
• 3c Czekelius C, Tzschucke CC. Synthesis 2010; 543
• 4 Bonge HT, Hansen T. Pure Appl. Chem. 2011; 83: 565
• 5a Bonge TH, Pintea B, Hansen T. Org. Biomol. Chem. 2008; 6: 3670
• 5b Bonge HT, Hansen T. Synthesis 2009; 91
• 5c Bonge HT, Hansen T. J. Org. Chem. 2010; 75: 2309
• 5d Bolsønes M, Bonge-Hansen HT, Bonge-Hansen T. Synlett 2014; 25: 221
• 6a Schnaars C, Hennum M, Bonge-Hansen T. J. Org. Chem. 2013; 78: 7488
• 6b Mortén M, Hennum M, Bonge-Hansen T. Beilstein J. Org. Chem. 2015; 11: 1944
• 7a Bartoli A, Chouraqui G, Parrain J.-L. Org. Lett. 2012; 14: 122
• 7b Rodier F, Rajzmann M, Parrain J.-L, Chouraqui G, Commeiras L. Chem. Eur. J. 2013; 19: 2467
• 7c Rodier F, Parrain J.-L, Chouraqui G, Commeiras L. Org. Biomol. Chem. 2013; 11: 4178
• 8a Gutsche CD. Org. React. 1954; 8: 364
• 8b Hauptmann S, Hirschberg K. J. Prakt. Chem. 1966; 34: 272
• 8c Gutsche CD, Redmore D In Carbocyclic Ring Expansion Reactions . Hart H, Karabastos GJ. Academic Press; New York: 1968: 81
• 8d Krow GR. Tetrahedron 1987; 43: 3
• 9a Hashimoto T, Naganawa Y, Maruoka K. J. Am. Chem. Soc. 2009; 131: 6614
• 9b Moebius DC, Kingsbury JS. J. Am. Chem. Soc. 2009; 131: 878
• 9c Hashimoto T, Naganawa Y, Maruoka K. J. Am. Chem. Soc. 2011; 133: 8834
• 9d Rendina VL, Kaplan HZ, Kingsbury JS. Synthesis 2012; 44: 686
• 10 Mao H, Tang Z, Hu H, Cheng Y, Zheng W.-H, Zhu C. Chem. Commun. 2014; 50: 9773
• 11a Brown HC, Wheeler OH, Ichikawa K. Tetrahedron 1957; 1: 214
• 11b Brown HC, Wheeler OH, Ichikawa K. Tetrahedron 1957; 1: 221
• 11c Finiels A, Geneste P. J. Org. Chem. 1979; 44: 1577
• 11d Prelog V, Kobelt M. Helv. Chim. Acta 1949; 32: 1187
• 12 About 10% only of racemic chiral compounds crystallize as conglomerate. CCDC 1410693 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
• 13 For instance, Shibatomi and co-workers have used sodium azide alkylthiols or cesium fluoride as nucleophiles to displace the chloride atom. See: Shibatomi K, Soga Y, Narayama A, Fujisawa I, Iwasa S. J. Am. Chem. Soc. 2012; 134: 9836