基于[2,2]对环芳烷骨架手性配体的设计、合成及其在不对称反应中的应用研究进展报告

该报告围绕[2,2]对环芳烷类骨架的手性化合物,设计并合成了一些具有应用潜力的环芳烷骨架手性配体并对其参与的不对称反应进行了研究。(1)手性含硫配体的设计合成及应用研究设计并合成了含有手性亚砜官能团的4,12-二取代手性膦-亚砜类配体。通过亚砜官能团的还原,还可以得到相应的膦-硫醚配体。膦-亚砜类配体在不对称烯丙基化反应中取得了48%ee,膦-硫醚类配体在不对称氢化中可取得85%ee。(2)柔性骨架氮膦配体的设计合成及应用研究在环芳烷的刚性骨架结构中引入柔性因素,设计了一类氮膦配体,以吡啶或喹啉为含氮配位官能团。这类配体在钯催化的烯丙基烷基化反应、铜催化的格氏试剂对共轭烯酮的不对称加成反应、钯催化的吲哚不对称傅克烷基化反应、钯催化的吲哚-2-甲酸酯不对称氮烷基化反应中均表现出优秀的活性和选择性。对反应结果的分析充分证明了苄位取代基所起的关键作用,它的引入使得配体结构的刚性因素增加,控制了中间体的构象。(3)双羟基[2,2]对环芳烷化合物及其衍生的单膦配体的合成及应用从延伸碳链的角度出发,合成到一种双酚羟基化合物,可以顺利得到氨基亚磷酸酯配体。这类配体在铜催化的非环状α-β不饱和酮的共轭加成反应中得到应用,取得了很好的结果(99%ee,95%ee),底物适用性也非常广泛。

Solid Synthesis and Crystal Structure of Compound[ (PPh_3 )_3,Cu_2MoOS_3]

A brown-red compound [( PPh_3 )_2Cu_2MoOS_3] was synthesized through a solid state reaction. The crystal is monoclinic, space group P2_1/c with α =19. 316(5), b=10. 46(1), c=24. 738(8) A, β=97. 01(2)°, V=4946(9) A￣3, Z=4. The unique Mo atom has a distorted tetrahedral coordination geometry, one Cu atom has a distorted tetrahedral coordination geometry, too, but the other has a trigonal planar environment. The core , Cu_2MoOS_3, shows a butterfly-like structure.

The Synthesis and Crystallographic Characterization of Heterotrimetallic Linear Complex of [Et_4N][ (Ph_3P)_2{CuS_2WS_2Fe} Br_2]

The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.