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70349126109
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note
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Of course, the resulting formamide can be recycled to amine and isonitrile, thus completing the cycle.
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18
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70349106663
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note
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13C), and high resolution mass spectra. All data are provided in the Supporting Information.
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19
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70349097054
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note
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The cognate product, which we don't isolate, is almost certainly the (syn) mono thio anhydride. It seems unlikely (but not impossible) that such an anhydride is performing acylation. The rapidity of our observed acylation in less hindered settings renders such an interpretation highly unlikely.
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20
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57349171593
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21
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note
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The electronic depiction suggested in going from 40→38 is not intended to address the issue of timing (concertedness).
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22
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70349107089
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note
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The initially low solubility of compound 42 in DCM did not affect the reactivity of this substrate. The reaction efficiently proceeded in DCM, DMF, or DCM/DMF (1:1/v:v) solvent systems without additional base.
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24
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62449152302
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For reviews describing recent advances in amide bond formation, see: (a)
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For reviews describing recent advances in amide bond formation, see: (a) Valeur, E.; Bradley, M. Chem. Soc. Rev. 2009, 38, 606.
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Hackenberger, C.P.R.1
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32
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70349147235
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note
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While quantitative comparisons are not yet available, we believe that the rate of interdiction relative to rearrangement of the thio FCMA renders it a superior acylating device relative to intermediates arising in carbodiimide methodology.
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