Fluoroallylic alcohols

Appropriately constructed fluoroallylic alcohols are attacked at the double bond by sodium borohydride with Sfj2 displacement of the hydroxyl group rather than the vmylic fluorine [47] (eqiiauon 36)... 

Catalytic hydrogenolysis of 1,1-difluorocyclopropanes occurs at the C2-C3 bond with partial retention of fluorine in the cases studied [49] (equation 38) In contrast, reduction of acetoxy 1,1 difluorocytlopropanes with lithium aluminum hydride occurs with loss of fluoride to give (3-fluoroallyl alcohols, often with high stereose lectivity [50] (equation 39) A further variant involving free radical intermediates produces allylidene difluorides after ring opening [5/] (equation 40)... 

High diastereoselectivity is found in the epoxidation of fluoroallylic alcohols with titanium(IV) isopropoxide and fert-butyl hydroperoxide337. The anomalous Sharpless asymmetric epoxidation has been used in the synthesis of L-erythro- and D-threo-sphingosines338. 

Catalytic amounts of TBAF promote the addition of organosilanes to carbonyl compounds. Examples of this approach include allylation of aldehydes to give allylic alcohols (eq 40) and the preparation of a-fluoroallylic alcohols from benzaldehyde (eq41). ... 

The details of trans-medium-ring cycloalkene synthesis by silver-ion-assisted opening of igiem-dihalogenobicyclo[n,l,0]alkanes have been presented. Solvolysis of chlorofluorocyclopropanes (352) is also assisted by silver ion, and it provides a useful route to fluoroallyl alcohols (353). ... 

An efficient access to (Z)-/l-fluoroallyl alcohols (382), based on the two carbon homologation of aromatic aldehydes by the Horner-Wadsworth-Emmons reaction with 2-(diethoxyphosphoryl)-2-fluoro-ethanethioic acid S-ethyl ester (381), followed by reduction with sodium borohydride, has been devepoped by Rolando and co-workers (Scheme 134). ... 

The strategy described above is applicable to fluorotris(trimethylsilyl)methane (157) it reacts with two molecules of benzaldehyde to give 2-fluoroallyl alcohol 158 (Scheme 5.40) [57]. The reaction involves five events in a single operation generation of a naked methyl anion, aldehyde addition, Peterson elimination, generation of a naked sp anion, and the second aldehyde addition. 

The chlorofluorination of 2-fluoroallyl and 2-chloroallyl alcohols,allyl acetates,and... 

The chlorofluorination of 2-fluoroallyl and 2-chloroallyl alcohols,166 290 allyl acetates,256 and 1-substituted methyl (Z)-2-chloroacrylates241 with hexachloromelamine and hydrogen fluoride has been investigated (see Table 19). 

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