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Chemistry · L5 · Sharpless Asymmetric Epoxidation Face-Selectivity

How the chiral tartrate ligand bound to titanium blocks one face of an anchored allylic alcohol's double bond, so the peroxide oxidant (TBHP) can only deliver oxygen to the open face — the same blocking logic as the quadrant model, at a titanium center instead of Rh/Ru.

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Allylic alcohol substrateHydroxyl anchors substrateto Ti(OiPr)4 centerTi–tartrate–alkoxide complex(chiral tartrate ester bound to Ti)tert-Butyl hydroperoxide(TBHP oxidant)Chiral pocket: which faceof the C=C is open?Steric clash withtartrate ester wingOxygen delivered fromTi-bound peroxideEpoxide productsingle enantiomer, high eeblocked faceopen face
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