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- Title
Stereoselective Activation of Small Molecules by a Stable Chiral Silene.
- Authors
Sun, Xiaofei; Hinz, Alexander; Kucher, Hannes; Gamer, Michael T.; Roesky, Peter W.
- Abstract
The reaction of the dilithium salt of the enantiopure (S)‐BINOL (1,1'‐bi‐2‐naphthol) with two equivalents of the amidinate‐stabilized chlorosilylene [LPhSiCl] (LPh=PhC(NtBu)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, CO2 and HCl. The reaction with S8 led to a Si=C bond cleavage and concomitantly to a ring‐opened product with imine and silanethione functional groups. The reaction with CO2 resulted in the cleavage of the CO2 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 CO2 and HCl to a Si=C bond is unprecedented.
- Subjects
SMALL molecules; CARBONYL group; FUNCTIONAL groups; CARBON dioxide; SCISSION (Chemistry); RING formation (Chemistry)
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 55, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202201963