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以恶唑啉为导向基团 ,通过邻位锂化方便地高非对映选择性地合成了一系列平面手性二茂铁硫恶唑啉、硒恶唑啉和膦恶唑啉配体 .应用于 1 ,3 二苯基烯丙基醋酸酯的烯丙基烷基化反应 ,ee值最高可达 99%,膦氮配体在烯丙基胺化反应中 ,ee值最高也可达 97%.此外 ,发现中心手性起到了决定产物ee值和绝对构型的作用 ,平面手性和中心手性的匹配在取得高对映选择性上是重要的 .设计合成的一类平面手性二茂铁修饰的手性口袋型双膦配体 ,由于有平面手性的辅助而具有更有效的诱导效应 .这类配体在前手性亲核试剂的不对称烯丙基化生成季碳氨基酸衍生物构及alpha 位双取代季碳酮反应中 ,ee值最高分别可达到 75 %和 95 %.设计合成的 1 ,1’ 二茂铁膦氮配体 ,在单取代的烯丙基醋酸酯的钯催化区域选择性及对映选择性的烯丙基烷基化及胺化反应中 ,显示了非常高的反应活性、区域选择性和对映选择性 .配体中BINOL羟基由于和苄胺存在分子间氢键而对反应的选择性起到了关键作用 ,并从实验上给予了证明
A series of planar chiral ferrocenethiooxazoline, selenoxazoline and phosphinoxazoline ligands were conveniently synthesized by di-ortho-lithiation with oxazoline-oriented groups. Applied to 1, 3 diphenyl allyl acetate allyl alkylation reaction, ee value up to 99%, phosphine nitrogen ligand in the allylamine reaction, the highest ee up to 97 %. In addition, it has been found that central chirality plays a role in determining the ee value and the absolute configuration of the product, and the matching between planar chirality and central chirality is important in achieving high enantioselectivity. A class of planar chiral Ferrocene-modified chiral pocket-type bisphosphine ligands, due to the help of planar chirality, have a more efficient induction effect.Asymmetric allylation of these ligands to prochiral nucleophiles to produce quaternary carbon Amino acid derivatives and the alpha-disubstituted quaternary carbon-ketone reaction, the highest ee value of up to 75% and 95%, respectively.Designed synthesis of 1, 1 ’ferrocenylphosphine nitrogen ligand, monosubstituted allyl acetate Palladium-catalyzed regioselectivity and enantioselective allylalkylation and amination of esters show very high reactivity Of regioselectivity and enantioselectivity. BINOL ligand in the presence of a hydroxyl group and benzylamine since intermolecular hydrogen bonds while the selectivity of the reaction play a key role, and proved experimentally given