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2, which is often invisible. See also ref 7a. For a similar system refer to: Buchman, G. W.; Morin, F. G. Can. J. Chem. 1977, 55, 2885-2892.
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0343487902
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note
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The required amount of YbPB cannot be shifted below 2.5 mol % even when 2.5 equiv instead of 5 equiv of phosphite is used.
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37
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0000555734
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and references therein
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Six-membered cyclic phosphites such as 2-methoxy[1,3,2]-dioxaphosphinane are known to favor a single chair conformation. That conformer exhibiting the phosphorus lone pair in a equatorial orientation (as in conformer 1c-III) is significantly stabilized over the corresponding conformer with a axial phosphorus lone pair. The analogous acyclic phosphites are not fixed in such a convenient conformation and therefore are destabilized. For a review of the stereochemical aspects of phosphorus-containing cyclohexanes see: Maryanoff, B. E.; Hutchins, R. O.; Maryanoff, C. A. Top. Stereochem. 1979, 11, 187-326, and references therein.
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41
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0343923758
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note
-
The HF/6-31G** optimized conformer 1c-II exhibits a slightly prolonged P=O and shortened P-O bonds as a consequence of the established anomeric effect.
-
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43
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MTBE = methyl tert-butyl ether
-
MTBE = methyl tert-butyl ether.
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