夏普莱斯不对称环氧化Sharpless epoxidation

把烯丙醇画成羟甲基在右下方的平面图：用 (−)-D-DET 时氧从上面进攻，用 (+)-L-DET 时从下面进攻。由所选酒石酸可预测产物构型，几乎所有烯丙醇 ee 都在 90% 以上。

Draw the allylic alcohol with the CH₂OH at lower right: (−)-D-DET delivers oxygen from the top face and (+)-L-DET from the bottom. The tartrate predicts the configuration, typically with ee above 90 %.

活性物种是二聚的钛–酒石酸配合物。烯丙醇和 TBHP 都与钛配位，过氧氧原子在手性环境中被递送到双键上；羟基的配位是选择性的关键，所以只适用于烯丙醇。加入分子筛除水可使钛用量降至催化量（5–10 mol%）。

The active species is a dimeric titanium–tartrate complex. Both the allylic alcohol and TBHP bind titanium, and the peroxide oxygen is delivered to the alkene within the chiral pocket; coordination of the hydroxyl is essential, so only allylic alcohols work. Molecular sieves allow catalytic titanium (5–10 mol %).

K. 巴里·夏普莱斯与香月勗于 1980 年报道。夏普莱斯因手性催化氧化与诺尔斯、野依良治共获 2001 年诺贝尔化学奖。环氧醇可经区域选择性开环转化为二醇、氨基醇等，广泛用于合成糖类、大环内酯和药物。

Reported by K. Barry Sharpless and Tsutomu Katsuki in 1980. Sharpless shared the 2001 Nobel Prize in Chemistry with Knowles and Noyori for chirally catalysed oxidations. Epoxy alcohols open regioselectively to diols and amino alcohols, serving syntheses of sugars, macrolides and drugs.