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This sequence of functional group manipulations was performed as reported in ref 12.
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Determined by Mosher ester analysis and ultimate conversion to 1.
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16244370781
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Remaining material appeared to be a number of decomposition products of the alkynal that could not be identified.
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Work in our laboratory has shown that this system is effective for the methylenation of sterically hindered ketones. Jeso, V.; Jamison, T. F. Unpublished results.
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Jeso, V.1
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16244423062
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Many alkyne-aldehyde couplings may be conducted in acetone without a decrease in yield. Nevertheless, a notable exception exists, that being an intramolecular, Ni-catalyzed alkyne-ketone coupling observed during studies directed toward the synthesis of terpestacin, ref 22.
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68
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16244412994
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note
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Ozonolysis was followed by exposure to dimethyl sulfide affording 9b and another product, determined to be the ozonide at terminal position. Treatment of the ozonide with triphenylphosphine promoted clean conversion to 9b, giving an 80% combined yield of 9b. Direct reductive workup with triphenylphosphine resulted in much lower yields. See Supporting Information for more detail.
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69
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16244416935
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note
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4c NMDPP emerged as a uniquely powerful promoter of asymmetric Ni-catalyzed coupling reactions.
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72
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note
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This approach is likely an oversimplification, as it ignores the effects of other stereogenic centers, e.g. those in the tether linking the alkyne and the aldehyde. Related experiments with other sets of diastereomers would directly test these influences and possibly result in further refinement (or revision) of the model proposed herein.
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75
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0000784039
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For an in-depth study of situations in which developing 1,3-interactions (syn-pentane-like) better account for the observed sense of stereoinduction in additions to chiral aldehydes than the Felkin-Anh model; see: Roush, W. R. J. Org. Chem. 1991, 56, 4151-4157.
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