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The concentration of the lithium amide, although expressed in units of molarity, refers to the concentration of the monomer unit (normality). The concentrations of THF and pyrrolidine are expressed as total solvent added.
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16
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1642298194
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The cis and trans adducts of 3 would be formed as racemates, four stereoisomers overall. If, for example, these species formed a statistical distribution of dimers, there would be a total of six spectroscopically distinct diastereomers and a much higher number of possible tetramers. By contrast, achiral adduct 7 would likely form only one dimer and two tetramers differing by the stereochemistry of chelation. Mixed dimerization with LiHMDS as described precludes much of this complexity.
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17
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0001755997
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If the saturation kinetics arose from quantitative formation of lithium pyrrolidide at high pyrrolidine concentration, the rate of the 1,2-addition by LiHMDS/pyrrolidine and n-BuLi/pyrrolidine would have been equivalent.
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32
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