Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)–H versus Fe(II)–Vinylidene

We report an iron system, Cp*Fe­(1,2-R₂PC₆H₄X), which controls the Markovnikov and anti-Markovnikov hydrostannation of alkynes by tuning the ionic metal–heteroatom bonds (Fe–X) reactivity. The sequential addition of nBu₃SnH to the iron–amido catalyst (1, X = HN^–, R = Ph) affords a distannyl Fe­(IV)–H species responsible for syn-addition of the Sn–H bond across the CC bond to produce branched α-vinylstannanes. Activation of the C­(sp)–H bond of alkynes by an iron–aryloxide catalyst (2, X = O^–, R = Cy) affords an iron­(II) vinylidene intermediate, allowing for gem-addition of the Sn–H to the terminal-carbon producing β-vinylstannanes. These catalytic reactions exhibit excellent regioselectivity and broad functional group compatibility and enable the large-scale synthesis of diverse vinylstannanes. Many new reactions have been established based on such a synthetic Fe–X platform to demonstrate that the initial step of the catalysis is conveniently controlled by the activation of either the tin hydride or the alkyne substrate.