Cheng Lei, Li Ming-Ming, Xiao Li-Jun, Xie Jian-Hua, Zhou Qi-Lin
J Am Chem Soc. 2018 Sep 19;140(37):11627-11630. doi: 10.1021/jacs.8b09346. Epub 2018 Sep 7.
We developed a highly regioselective addition of 1,3-dienes with simple ketones by nickel-hydride catalyst bearing DTBM-SegPhos ligand. A wide range of aromatic and aliphatic ketones directly coupled with 1,3-dienes, providing synthetically useful γ,δ-unsaturated ketones in high yield and regioselectivity. The asymmetric version of the reaction was also realized in high enantioselectivity by using novel chiral ligand DTBM-HO-BIPHEP. The utility of this hydroalkylation was demonstrated by facile product modification and enantioselective synthesis of ( R)-flobufen.
我们通过带有DTBM-SegPhos配体的氢化镍催化剂，实现了1,3 - 二烯与简单酮的高区域选择性加成反应。多种芳香族和脂肪族酮可直接与1,3 - 二烯偶联，以高收率和区域选择性提供具有合成价值的γ,δ - 不饱和酮。通过使用新型手性配体DTBM-HO-BIPHEP，该反应的不对称版本也实现了高对映选择性。这种氢烷基化反应的实用性通过产物的简便修饰以及（R）-氟比洛芬的对映选择性合成得到了证明。
