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We were inspired initially by the common water-soluble disulfide reducing agent, tris(2-carboxyethyl)phosphine (TCEP) (Houk, J.; Whitesides, G. M. J. Am. Chem. Soc. 1987, 109, 6825-6836). Accordingly, we synthesized the water-soluble bis(2-carboxyethyl)thiomethyl phosphine but found its mediation of traceless Staundinger ligations in water to yield a preponderance of amine byproduct (data not shown).
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We were inspired initially by the common water-soluble disulfide reducing agent, tris(2-carboxyethyl)phosphine (TCEP) (Houk, J.; Whitesides, G. M. J. Am. Chem. Soc. 1987, 109, 6825-6836). Accordingly, we synthesized the water-soluble bis(2-carboxyethyl)thiomethyl phosphine but found its mediation of traceless Staundinger ligations in water to yield a preponderance of amine byproduct (data not shown).
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Like the iminophosphorane phosphorus, the thioester carbon becomes more electrophilic and hence susceptible to hydrolysis upon protonation of the iminophosphorane. Thioester hydrolysis would decrease the yield of amide 16 in a pH-dependent manner and is thus consistent with the data in Figure 1.
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Like the iminophosphorane phosphorus, the thioester carbon becomes more electrophilic and hence susceptible to hydrolysis upon protonation of the iminophosphorane. Thioester hydrolysis would decrease the yield of amide 16 in a pH-dependent manner and is thus consistent with the data in Figure 1.
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