中文摘要：

以（R）或（S）-H8-BINOL为配体骨架，合成具有螺旋结构C3对称的六个新型单齿亚磷酸酯配体，并将它们首次成功应用于Rh（acac）（CO）2催化苯乙烯的不对称氢甲酰化，和Cu（OTf）2催化二乙基锌对链烯酮的不对称1，4-共轭加成反应研究中.在铑催化苯乙烯的不对称氢甲酰化反应中，螺旋结构C3对称的单齿亚磷酸酯配体给出高的催化活性（转化率93%）和支链醛/直链醛区域选择性（b/n=95/5），和较低的对映选择性[28% ee （R）].在铜催化二乙基锌对链烯酮的不对称1，4-共轭加成反应中，以查尔酮为底物筛选配体，优化反应条件；在优化的反应条件下，考察11种不同结构链状烯酮底物对反应的适应性；以Cu（OTf）2作为催化剂前体，乙醚为溶剂，在-20℃，配体（R）-3中大位阻金刚烷基和（R）-H8-联萘基团之间的空间结构匹配是获得98%分离产率和72%（R）对映选择性的关键因素，产物绝对构型主要由配体结构中H8-联萘基团的构型决定.研究结果证明C3对称的新型单齿亚磷酸酯配体在不对称氢甲酰化和1，4-共轭加成反应中具有应用潜力.

英文摘要：

A family of the novel chiral helical C3-symmetric monophosphite ligands has been synthesized from axially chiral （R）-or （S）-H8-BINOL and PCl3. The performance of these ligands in asymmetric catalysis was evaluated by the Rh-catalyzed asymmetric hydroformylation of styrene, and the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to acyclic enones. The catalytic hydroformylation of styrene gave rather high conversion （93%）, high regioselectivity （b/n=95/5） and low enantioselectivity[28% ee （R）] using ligand （R）-2 in tetrahydrofuran at room temperature. Under the optimal 1,4-conjugate addition of ZnEt2 to chalcone 3a conditions, eleven acyclic enones 4a-4k were all converted smoothly to the 1,4-adducts with high enantiomeric excess. Using Cu（OTf）2 as catalyst precursor and Et2O as solvent at -20℃, the structure of ligand （R）-3 comprising a partially hydrogenated 2,2＇-（1,1＇-binaphthyl）-phosphite scaffold and an adamantyl moiety was key factor in improving catalytic activity and the enantioselectivity with up to 98% yield and 72% ee （R）. The sense of enantiodiscrimination of the reaction was controlled by the configuration of the diaryl phosphite moieties.