Synthesis of functionalized CF3-containing heterocycles via [2,3]-sigmatropic rearrangement and sequential catalytic carbocyclization

Daria V. Vorobyeva (1) , Artur K. Mailyan (1) , Alexander S. Peregudov (1) , Natalia M. Karimova (1) , Tamara P. Vasilyeva (1) , Ivan S. Bushmarinov (1) , Christian Bruneau (2) , Pierre H. Dixneuf (2) , Sergey N. Osipov (1)

1 INEOS - A. N. Nesmeyanov Institute of Organoelement Compounds
2 ISCR - Institut des Sciences Chimiques de Rennes

A new efficient access to functionalized CF3-substituted and nitrogen or sulfur-containing heterocycles has been developed directly from diazocompounds CF3C(N2)Z (Z=CO2Me, P(O)(OEt)2). The method is based on the direct selective synthesis of doubly unsaturated substrates followed by metal-mediated carbocylization. The first step has been performed by Cu(II)-catalyzed [2,3]-sigmatropic rearrangement of propargyl- or/and allyl-containing sulfur and nitrogen ylides leading to fluorinated enynes, diolefins, and especially allenynes derivatives. The second step involves their carbocyclization via ring closing metathesis and Pauson-Khand reaction.

Mots clés: Fluorinated diazocompounds; Sigmatropic rearrangement; Allenynes; Enynes; Catalysis; Carbocyclization; Heterocycles

Domaines: Catalyse

Daria V. Vorobyeva, Artur K. Mailyan, Alexander S. Peregudov, Natalia M. Karimova, Tamara P. Vasilyeva, et al.. Synthesis of functionalized CF3-containing heterocycles via [2,3]-sigmatropic rearrangement and sequential catalytic carbocyclization. Tetrahedron, 2011, 67, pp.3524-3532. ⟨10.1016/j.tet.2011.03.031⟩. ⟨hal-00631721⟩