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We report a novel conjugation of N‐terminal cysteines (NCys) that proceeds with fast kinetics and exquisite selectivity, thereby enabling facile modification of NCys‐bearing proteins in complex biological milieu. This new NCys conjugation proceeds via a thiazolidine boronate (TzB) intermediate that results from fast (k2: ≈5000 m−1 s−1) and reversible conjugation of NCys with 2‐formylphenylboronic...
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