99421-71-3Relevant academic research and scientific papers
Alkylation of isatins with trichloroacetimidates
Chisholm, John D.,Joshi, Bhaskar D.,Mate, Nilamber A.,Meador, Rowan I. L.
, p. 2131 - 2136 (2022/03/31)
N-Alkylation of isatins can be achieved utilizing trichloroacetimidate electrophiles and a Lewis acid catalyst. These reactions provide access to N-alkyl isatins, versatile scaffolds which are often employed in the synthesis of pharmaceutical lead structures as well as natural products. Secondary trichloroacetimidates that are precursors to stabilized carbocations provided excellent yields of the isatin product. Substitution was well tolerated on the isatin, although reduced reactivity was observed with C7-substitution, likely due to the steric effects. Solvent effects can be used to favor O-alkylation under similar reaction conditions.
Rearrangement of Benzylic Trichloroacetimidates to Benzylic Trichloroacetamides
Adhikari, Arijit A.,Suzuki, Tamie,Gilbert, Reesheda T.,Linaburg, Matthew R.,Chisholm, John D.
, p. 3982 - 3989 (2017/04/11)
The rearrangement of allylic trichloroacetimidates is a well-known transformation, but the corresponding rearrangement of benzylic trichloroacetimidates has not been explored as a method for the synthesis of benzylic amines. Conditions that provide the tr
Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions
Wallach, Daniel R.,Chisholm, John D.
, p. 8035 - 8042 (2016/09/12)
An intermolecular alkylation of sulfonamides with trichloroacetimidates is reported. This transformation does not require an exogenous acid, base, or transition metal catalyst; instead the addition occurs in refluxing toluene without additives. The sulfonamide alkylation partner appears to be only limited by sterics, with unsubstituted sulfonamides providing better yields than more encumbered N-alkyl sulfonamides. The trichloroacetimidate alkylating agent must be a stable cation precursor for the substitution reaction to proceed under these conditions.
Nucleophilic substitution catalyzed by a supramolecular cavity proceeds with retention of absolute stereochemistry
Zhao, Chen,Toste, F. Dean,Raymond, Kenneth N.,Bergman, Robert G.
supporting information, p. 14409 - 14412 (2015/02/02)
While the reactive pocket of many enzymes has been shown to modify reactions of substrates by changing their chemical properties, examples of reactions whose stereochemical course is completely reversed are exceedingly rare. We report herein a class of wa
A novel synthesis of isocyanates and ureas via β-elimination of haloform
Braverman,Cherkinsky,Kedrova,Reiselman
, p. 3235 - 3238 (2007/10/03)
A novel synthesis of isocyanates via base-induced β-elimination of haloform from N-monosubstituted trihaloacetamides is described. The rate of reaction exhibits a strong dependence on the nature of the trihalomethyl group. Thus, while the reaction of tribromoacetamides proceeds at room temperature and the reaction of trichloroacetamides requires heating in polar solvents, no reaction could be observed for any of the corresponding trifluoro derivatives. This novel β-elimination of haloform from stable and readily available trihaloacetamides was applied to a 'one-pot' synthesis of ureas which avoids the use of phosgene and isolation of isocyanates.
