C-allyl-S-

C10H16NO9S2--K+H2O C-Allyl-S-/J-D-glucopyranosyl-0-sulfo(thiocarbohydroximi- KMYRMH01, 38 440... 

C,oH16N09S2 K+-H20 C-Allyl-S-/3-D-glucopyranosyl-0-sulfo(thiocar-bohydroximidate), potassium salt, monohydrate ( sinigrin ) (KMYRMH01)58... 

Since allylation with allylic carbonates proceeds under mild neutral conditions, neutral allylation has a wide application to alkylation of labile compounds which are sensitive to acids or bases. As a typical example, successful C-allylation of the rather sensitive molecule of ascorbic acid (225) to give 226 is possible only with allyl carbonate[l 37]. Similarly, Meldrum s acid is allylated smoothly[138]. Pd-catalyzed reaction of carbon nucleophiles with isopropyl 2-methylene-3,5-dioxahexylcarbomite (227)[I39] followed by hydrolysis is a good method for acetonylation of carbon nucleophiles. 

Various S-nucleophiles are allylated. Allylic acetates or carbonates react with thiols or trimethylsilyl sulfide (353) to give the allylic sulfide 354[222]. Allyl sulfides are prepared by Pd-catalyzed allylic rearrangement of the dithio-carbonate 355 with elimination of COS under mild conditions. The benzyl alkyl sulfide 357 can be prepared from the dithiocarbonate 356 at 65 CC[223,224]. The allyl aryl sufide 359 is prepared by the reaction of an allylic carbonate with the aromatic thiol 358 by use of dppb under neutral condi-tions[225]. The C-allyl phosphoro- or phosphonothionate 360 undergoes the thiono thiolo allylic rearrangement (from 0-allyl to S-allyl rearrangement) to afford 361 and 362 at 130 °C[226]. 

With 1,1-difluorocyclopropabenzene and a range of nickel(O) complexes, nickelabicy-clobutanes 118 (84—93%) are formed by loss of olefin or phosphane ligands and addition of the nickel atom across the bridge bond (Scheme 20)256-266. The products appear to be stable at ambient temperatures but are oxygen sensitive the majority revert to cycloproparene in solution even below -20 °C. With (j -allyl)( s-cyclopentadienyl(palladium in the... 

Entry Allyl silane a,g-Enone Temp., °C, time S,e-Enone % yield) 3 ... 

However the epoxidation of olefins lacking allylic and other reactive C-H bonds with molecular oxygen has recently been achieved on silver catalysts (Table 1). In 1997 the Eastman Chemical Company started the manufacture of 3,4-epoxy-1-butene, the product of mono-epoxidation of butadiene, on a semiworks production scale (entry 1). Remarkably enough the presence of benzylic hydrogen, as in / -methyl styrene (entry 5), drives the oxidation towards combustion, while sterically hindered allylic C-H s, as in norbornene (entry 6), are inert to oxidation. 

Reaction with R SiHCl S.8.3.2.4 Reaction with RjSn, SnXj S.8.S.8.3 Reaction with C-C4R2X2 S.8.2.9.S Reaction with Hg(SiMe3)2. S.8.3.S.2 Reaction with allyl halides S.8.2.9.4 Reaction with disilacyclobutene S.8.3.6.1... 

Mayton, H.S., Olivier, C., Vaughn, S.R and Loria, R. (1996) Correlation of fungicidal activity of Brassica species with allyl isothiocyanate production in macerated leaf tissue. Phytopathology, 86,267-71. 

Hanessian, S., Yang, H., and Schaum, R., Hydrogen-bonding as a stereocontrolling element in free-radical C-allylation reactions Vicinal, proximal, and remote a.symmetric induction in the amino acid series, J. Am, Chem. Soc. 118, 2507-2508 (1996). 

There are few reports of the transition metal complex-catalyzed isomerization of S-allyl sulfides and sulfones. This is clearly a consequence of the very strong coordinating ability of sulfur atoms and the resulting tendency for S-C (allyl) bond cleavage. In the case of a bulky substituent being present at the sulfur atom, the isomerization to 1-propenyl derivatives is successful (Eqs. 12.14 and 12.15) [20]. 

Oxidative cleavage of C-allyl mannose 419 [157] following Wong s procedure [158] leads to acid 420 which is esterifled with 418 prior to methylenation with Tebbe s reagent (O Scheme 83). 

The [l-i C] 234b, [2- C] 234b, [4- C] 234b and [6- C] 234b (with specific activities in the range 4-8 mCimmoP ) have been prepared in the reaction sequence shown in equation 95 using [ C] Eschenmoser s salt labelled in the methylene group, dimethyl [2- C]diazomalonate (equation 96), [1- C] allyl alcohol and [3- C] allyl alcohol. ... 

In the latter case the S N allyl group migration is only efficient when Pd catalysis is employed, otherwise, at much higher temperatures, a double bond isomerization occurs first and is then followed by an S C allyl shift by means of a thio-Claisen rearrangement. As the appropriate 5-allyl thioimidates are easily prepared by alkylation of thioamides with allyl halides, the overall process is an 5n substitution of an allylic halide by an amine, a reaction which is difficult to achieve directly. 

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