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3B (5 equiv) also yielded recovered 1a. When this reaction was conducted in the presence of i-PrI (5 equiv), reduced product 3a was obtained in 60% yield (see the second entry of Table 1).
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25444449416
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1H NMR spectra to those of 1a and 1b. The olefinic proton of the E-isomers resonates at 8.1-8.0 ppm, whereas in the Z-isomers it resonates at 7.6-7.5 ppm.
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45
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1H NMR spectra to that of 6a. The olefinic protons of these compounds resonate at 8.02-8.01 ppm, consistent with the chemical shifts of the corresponding protons in E-1a-c.
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1H NMR spectra recorded immediately after isolation of d-7a-c exhibited amide N-H signals attenuated by an amount consistent with the extent of proton incorporation at the α-position. Over time, the N-bound deuterium exchanged with protons derived from adventitious moisture and the amide signals returned to their normal levels of intensity. Attempts to block this exchange by performing radical conjugate additions on protected or tertiary amides were unsuccessful; the N-Boc derivative of 6a afforded reduction product exclusively, whereas N-PMB and N-Me versions were unreactive.
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For a discussion of the effect of molecular sieves on chiral Lewis acids, see ref 23b.
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1H NMR spectra to those of 2b. Specifically, the α- and β-protons of the syn isomers each resonated 0.15-0.20 ppm upfield from the corresponding protons of the anti isomers, and the syn-isopropyl methine resonated ca. 0.20 ppm downfield from the anti-isopropyl methine.
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