手性的H'_4-NOBIN衍生物在不对称加成和取代反应中的应用

Application of Chiral H'_4-NOBIN Derivatives to Asymmetric Addition and Allylation

以手性H'4-NOBIN为原料合成了新型手性氨基酚2和N,P配体5,并将化合物2应用于催化二乙基锌对醛的不对称加成反应,产率达90%,对映体过量最高为45.9%ee.化合物5用于钯催化的1,3-二苯基-2-烯丙基乙酸酯的不对称烯丙基烷基化反应,产率为89%,对映体过量最高为81.6%ee.结果表明氨基酚2手性诱导作用弱于未氢化的NOBIN,但却高于其八氢衍生物,而N,P配体5给出相反的结果.

Two chiral ligands （aminol and aminophosphine） derivatived from （R）-H＇4-NOBIN were prepared. Chiral amino phenol 2 was employed as a catalyst in the asymmetric addition reaction of diethylzinc to aldehydes with the yield up to 90% and enantiomeric excesses up to 45.9% ee. Chiral N,P ligand 5 was examined for the asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with up to 89% yield and up to 81.6% ee. The results showed the H＇4-NOBIN derivatives provided weaker chiral inducement than the parent compound but better induction than H8-NOBIN derivatives, while the chiral N,P ligand 5 displayed opposite results.