Stereoselective Activation of Small Molecules by a Stable Chiral Silene

The reaction of the dilithium salt of the enantiopure ( S )‐BINOL (1,1’‐bi‐2‐naphthol) with two equivalents of the amidinate‐stabilized chlorosilylene [L Ph SiCl] (L Ph =PhC(N t Bu) 2 ) led to the formation of the first example of a chiral cyclic silene species comprising an ( S )‐BINOL ligand. The reactivity of the Si=C bond was investigated by reaction with elemental sulfur, CO 2 and HCl. The reaction with S 8 led to a Si=C bond cleavage and concomitantly to a ring‐opened product with imine and silanethione functional groups. The reaction with CO 2 resulted in the cleavage of the CO 2 molecule into a carbonyl group and an isolated O atom, while a new stereocenter is formed in a highly selective manner. According to DFT calculations, the [2+2] cycloaddition product is the key intermediate. Further reactivity studies of the chiral cyclic silene with HCl resulted in a stereoselective addition to the Si=C bond, while the fully selective formation of two stereocenters was achieved. The quantitative stereoselective addition of CO 2 and HCl to a Si=C bond is unprecedented.