Stilbene oxide epoxide ring opening

The aryl meio-epoxide, c -stilbene oxide, is ring-opened by substituted anilines at 0°C in dichloromethane in the presence of 4 A molecular sieves and a (R)-(+)-BINOL-Sc(OTf)3-A-methylmorpholine complex giving )0-amino alcohols in yields ranging from 78 to 92% with 64-94% The aliphatic meso-epoxide, cyclcohexane i oxide, gave 96% of the / -amino alcohol but with only 22% ee. 

Reactions of 1 with epoxides involve some cycloaddition products, and thus will be treated here. Such reactions are quite complicated and have been studied in some depth.84,92 With cyclohexene oxide, 1 yields the disilaoxirane 48, cyclohexene, and the silyl enol ether 56 (Eq. 29). With ( )- and (Z)-stilbene oxides (Eq. 30) the products include 48, ( > and (Z)-stilbenes, the E- and Z-isomers of silyl enol ether 57, and only one (trans) stereoisomer of the five-membered ring compound 58. The products have been rationalized in terms of the mechanism detailed in Scheme 14, involving a ring-opened zwitterionic intermediate, allowing for carbon-carbon bond rotation and the observed stereochemistry. 

Desymmetrization with halogen nucleophiles was effectively demonstrated with two mechanistically-divergent chiral catalysts. Denmark disclosed a Lewis-base activated delivery of chloride that was catalyzed by the enantiopuxe phos-phoramide 16. Binding of the phosphoramide was believed to induce dissociation of SiCl4 into the chiral phosphorus/silicon cation and chloride anion, which subsequently ring-opened the activated epoxide. The best enantioselectivity was observed with cfs-stilbene oxide, which was formed in 94% yield and 87% ee (Scheme 14) [28]. 

The product of the reaction with c/s-stilbene was a trichloroacetate ester which yielded the wcso-glycol upon reduction with lithium aluminium hydride the /raHs-olefin yielded the racemic glycol after the same treatment . Such reaction products are consistent with ring-opening of the epoxide by strong acid, and it was shown that (-)-rraHs-stilbene oxide reacted rapidly (relative to the rate of epoxidation) with trichloroacetic acid in benzene the overall observations are indicative of acid-catalysed epoxidation of stilbene but may admit other interpretations, one of which involves thermodynamic intervention of trichloroacetic acid dimer in a solvating capacity rather than in a truly kinetic function. 

Ring opening of oxiranes is catalyzed by zirconium or hafnium complexes in the presence of nucleophiles. Cp2ZrCl2 was used as a catalyst for ring opening of substituted epoxides with alcohols under mild conditions. The corresponding alkoxyalcohols were obtained in good yields. As shown in Equation 38, when trans-stilbene oxide was subjected to the reaction in methanol, a mixture of anti-and syn isomers were obtained [43]. 

In addition, this class of chiral phosphoramides could catalyze the enantioselective ring opening of epoxides with silicon tetrachloride (SiCfl) [4]. For instance, the reaction of ds-stilbene oxide with SiCl, proceeded smoothly in the presence of 1 to afford the desired chlorohydrin in an enantiomericaUy enriched form (Scheme 7.3). The reactive ion pair shown in the scheme was proposed to be generated through the activation of SiCl, by the coordination of one phosphoramide 1, serving to activate the epoxide it was confirmed that bis-phosphoramide 2 was far less selective in this reaction. 

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