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For the general aspects of the conformation (s-cis vs s-trans) of unsaturated carbonyl compounds, see: Stereochemistry of Organic Compounds; Eliel, E. L., Wilen, S. H., Eds.; John Wiley & Sons: New York, 1994; Chapter 10.2., pp 615 and 622. Also see the depiction below for two major conformations of an α,β-unsaturated carbonyl compound and diene, respectively. The definition for the conformations (s-trans and s-cis, where "s" denotes a "single bond") of an extended dienolate is based on that for a diene. equation presented
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1H NMR shifts exactly corresponding to 1:1 complexes between ATPH and carbonyl compounds. A slow exchange between free and bound substrates on a NMR time scale caused neither shifts of free carbonyl compounds nor average shifts between these substrates.
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In fact, a rapid equilibrium (s-trans ⇄ s-cis, for example, see Figure 6) faster than the rate of aldolization is envisioned by complete reversal of the olefin configuration (the E-γ-methyl of -15 was delivered to the Z-γ-methylene of 20).
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72
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As one of the referees suggested, significant effects of the second equivalent of ATPH, which presumably activates the aldehyde partner, need further investigation. In the absence of the second ATPH, a considerable decrease in chemical yields was consistently observed.
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