上海有機所合成讲义第7讲.pptVIP

控制因素 Stereoelectronic Effects - The attacking electrophile must obey the principle of maximum overlap of the participating orbitals by perpendicular approach to the plane of atoms which constitute the enolate (enol) function.;;;; Steric Effects;ii) Diastereoselectivity;;;;;; Endocyclic Enolates;;iii) Other Conformationally Inflexible Systems;;;;iV) Conjugate Addition/Alkylation: Stereochemistry;iii) Asymmetric Alkylations;;;;;;;§ 5-2 Aldol Addition (Condensation);§ 5-2-2 立体化学 A. 非手性的醛与非手性烯醇盐;syn:anti 98:2;- Zimmerman-Traxler Model ( J. Am. Chem. Soc. 1957, 79, 1920) - Chair-like, closed transition state: metal coordination to both carbonyls;Transition state;b. R1/R3 增大，非对映选择性提高(Syn选择性);c. 金属离子也影响反应的非对映选择性，使用硼时选择性往往会变好，其原因可能是能形成更紧密的过渡态 (B–O 更短, R1/R3 立体作用增大所致)。 ;Masamune Tetrahedron Lett. 1979, 1665.;d.当R2很大时，R3/R2立体作用比R1/R3作用可能会更强， 有时会导致立体化学反转.;e. Z-型烯醇盐得到的非对映选择性 (for syn aldol)比 E-型烯醇盐 (for anti).;f. 立体化学的控制 Z/E 异构体的控制-利用羰基化合物或试剂结构的差异以及反应条件的不同; E-烯醇硼盐的制备;More Examples;Brown J. Org. Chem. 1994, 59, 2336.;Brown J. Am. Chem. Soc. 1989, 111, 3441.;B. 手性的醛与非手性烯醇盐的Aldol缩合;;;b. Chelation Control;without chelation control;C.非手性的醛与手性烯醇盐的Aldol缩合; Origin of diastereoselectivity;For the alternative enantiomer;;Control of Selectivity;;使用1 eq. 的Ag+和 1 eq. 也可调控