DBU-Promoted Deaminative Thiolation of 1 H -Benzo[ d ]imidazol-2-amines and Benzo[ d ]oxazol-2-amines.

A facile and efficient catalyst-/metal-/oxidant-free DBU-promoted deaminative thiolation reaction of 1 H -benzo[ d ]imidazol-2-amines and benzo[ d ]oxazol-2-amines has been developed at room temperature conditions in a one-pot protocol. This practical three-component strategy represents a novel and environmentally friendly reaction pathway toward the straightforward synthesis of various 2-thio-1 H -benzo[ d ]imidazoles and 2-thiobenzo[ d ]oxazoles using carbon disulfide as a sulfur source through C-N bond cleavage and C-S bond formation process. Different types of 1 H -benzo[ d ]imidazol-2-amines, benzo[ d ]oxazol-2-amines, and organic bromides are suitable substrates. The gram-scale and late-stage modification experiments provide the potential applications based on this methodology in the field of organic and medicinal chemistry.