Atomic Pt-Catalyzed Heterogeneous Anti-Markovnikov C–N Formation: Pt10 Activating N–H for Pt1δ+-Activated C═C Attack

C–N formation is of great significance to synthetic chemistry, as N-containing products are widely used in chemistry, medicine, and biology. Addition of an amine to an unsaturated carbon–carbon bond is a simple yet effective route to produce new C–N bonds. But how to effectively conduct an anti-Markovnikov addition with high selectivity has been a great challenge. Here, we proposed a strategy for highly regioselective C–N addition via hydroamination by using supported Pt. It has been identified that atomic-scale Pt is the active site for C–N addition with Pt12+ for Markovnikov C–N formation and atomic Pt (Pt1δ+ and Pt10) contributing to anti-Markovnikov C–N formation. A selectivity of up to 92% to the anti-Markovnikov product has been achieved with atomic Pt in the addition of styrene and pyrrolidine. A cooperating catalysis for the anti-Markovnikov C–N formation between Pt1δ+ and Pt10 has been revealed. The reaction mechanism has been studied by EPR spectra and in situ FT-IR spectra of adsorption/desorption of styrene and/or pyrrolidine. It has been demonstrated that Pt10 activates amine to be electrophilic, while Pt1δ+ activates C═C by π-bonding to make β-C nucleophilic. The attack of nucleophilic β-C to electrophilic amine affords the anti-Markovnikov addition. This strategy proves highly effective to a variety of substrates in anti-Markovnikov C–N formation, including aromatic/aliphatic amines reacting with aromatic olefins, aromatic/aliphatic olefins with aromatic amines, and linear aliphatic olefins with secondary aliphatic amines. It is believed that the results provide evidence for the function of varied chemical states in monatomic catalysis.