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The p-methoxbenzyl protecting group could not be removed later in the synthesis because of competing oxidation of the unsaturated thiazole and so had to be replaced at this stage.
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8
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The ease of olefination of lactols derived from pantolactone was found to depend on the O-protecting group, compare the synthesis of 27 and 83. In some cases, the Wittig reagent was fine, but in others less satisfactory results were obtained and so alternative reagents had to be used. This behavior of the different lactols may depend on the rate of equilibration between the lactol and the open-chain hydroxyaldehyde.
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A transition state analogous to that shown in 73 but with the group α to the metal in the axial position is consistent with the behavior of allylstannanes (see [1]). The preference for the group α to the metal to adopt either the axial or equatorial position may be determined by the preferred conformation of the intermediate, i.e., the preference for the oxygen ligand of the metal to adopt an apical position. Alternatively, the preference of allylstannanes to give (Z)-alkenes exclusively for 1,5-, 1,6 and 1,7-stereocontrol may be indicative of a two-step process for the reaction between the allyltin trihalide and an aldehyde, the first step being a displacement on the tin of the coordinating oxygen substituent by the aldehyde followed by allyl group transfer in a separate step. Studies into the structures of the intermediates may help to resolve this dichotomy.
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