Insertion reactions fluoroolefins

Finally, along with electrophilic reactions involving a C=C bond, typical of both hydrocarbon and polyfluorinated olefins, there is another group of transformations which is specific for fluoroolefins only - reactions involving an allylic C-F bond. This group of reactions includes (but is not limited to) such processes as migration of the double bond in fluoroolefins or insertion reactions, as shown in Eq. (4), leading to F-allyl fluorosulfate (2) [5] ... 

First indication that the course of the reaction of S03 with fluoroolefins could be different was found in 1976. The reaction of polyfluorocyclobutenes with stabilized sufur trioxide results in insertion reaction and produces the corresponding fluorosufates 86a-c [174] ... 

The reaction is reversible. If a fluorinated olefin is used, it would be expected that the resulting fluoroalkyl compound would be readily obtained, since the greater strength of the metal-fluorocarbon bond as compared to the metal-hydrocarbon bond favors the insertion reaction 267). The reaction of hydroplatinum(II) complexes with fluoroolefins has been extensively studied. A surprising product from a number of these reactions is a fluorovinyl compound rather than the anticipated fluoroalkyl complex. In Fig. 4 are shown the reactions of PtHCl(PEt3)2 with a series of fluoroolefins to give PtCl(CF=CF2)(PEt3)2 (XXXIV)... 

The preparations of Glyi/r[CF=CH]Gly (4) and Phei/r[CF=CH]Gly (5) were described by Allmendinger and his coworkers [46,47]. The Gly-Gly fluoroolefin dipeptide isostere (4) was synthesized from cyclic acetal (6), obtained by the procedure of Dehmiow [48] involving a carbene insertion and reexpansion reaction. Further elaboration as detailed in Scheme 1 ultimately afforded the A/-protected amino acids (4). 

The reactions of difluorosilylene with olefins and fluoroolefins [e.g., Eqs. (46) and (47)] appear to proceed by quite different pathways. Similarly, the reaction with benzene resulted in addition products (71, 107) [Eq. (49)], whereas reaction with fluorobenzene led to insertion products (107) [Eq. (50)]. 

Irradiation of Au(CH3)L (L = PPh3 or PPh2Me) in the presence of the fluoroolefins C2F4, C3F6, and C2F3CI has been reported to give insertion products of the type 137 [Eq. (128)] 159). Similar reaction with hexa-... 

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