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[16a] assuming that this isomer arises from facial selectivity in the aldol reaction and not as a consequence of the E configuration of the enolate group of 10. Similarly, the stereochemistry assigned as the syn,syn products 14 was not proven in each case. Those assignments also rely to varying extents on the examples given in ref. [16a].
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The Noyori reduction of various diketo esters was very dependent on the amount of acid in the reaction mixture. Without the presence of stoichiometric acid, the rate of reduction and the selectivity dropped in the reduction. At higher pressures, the chemoselectivity of the reduction was poor resulting in reduction of both of the alkene groups. Furthermore, the carbonyl group at C5 was never reduced under these conditions, but was absolutely necessary for the reduction of the carbonyl group at C3. When an alcohol functionality was at C5, no reduction was seen. A. Balog, unpublished results.
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