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We originally attributed this regioselective outcome to additional steric hindrance provided by the ethyl substituent of triene substrate 19. However, the asymmetric dihydroxylation of triene i also provided a 5 : 1 mixture of dihydroxylation products ii and iii, and dihydroxylation of the internal trisubstituted alkene of i was not observed. Presumably the internal trisubstituted alkenes of substrates 19 and i are protected from dihydroxylation by polyene folding in the protic solvent medium. See also: Van Tamelen, E. E.; Sharpless, K. B. Tetrahedron Lett. 1967, 2655. Chemical equations presented.
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Initial attempts to achieve syn-oxidative cyclization by reaction of diol-alkene 26 with acylperrhenate reagents were unsuccessful and appeared to give product iv as a single diastereomer. This unexpected product presumably arises from secondary alcohol oxidation and acid-catalyzed pinacol-type rearrangement. The principal difference between substrate 26 and other substrates which we had previously successfully cyclized (ref. 12) appears to be the presence of the tertiary hydroxyl group. Chemical equations presented.
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39
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0342496048
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note
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17 (8 : 1 selectivity) as the result of chelate-controlled hydride addition (note that the ethyl substituent exerts a greater steric effect than the ring methylene). Reduction of 27 with sodium borohydride alone exhibited no stereoselectivity.
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40
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