Rh(III)-Catalyzed Diastereoselective C-H Bond Addition/Cyclization Cascade of Enone Tethered Aldehydes.
Rh(III)-Catalyzed Diastereoselective C-H Bond Addition/Cyclization Cascade of Enone Tethered Aldehydes.
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DOI：
10.1039/c5sc04138d
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发表时间：
2016-02-01
期刊：
影响因子：
8.4
通讯作者：
Ellman JA
中科院分区：
文献类型：
--
作者：
Boerth JA;Ellman JA
Rh(iii) 催化 C-H 键在烯烃和羰基 π-键上级联加成，形成两个新的 σ C-C 键。报道了 Rh(iii) 催化的 C-H 键在烯烃和羰基 π-键上的级联加成。该反应在温和的反应条件和低催化剂负载下进行。一系列导向基团被证明是有效的，除了芳香族 C(sp2)-H 键之外，烯基的官能化也是如此。当烯酮和醛亲电体连接在一起时，得到具有三个连续立体中心的环状β-羟基酮，具有高非对映选择性。醛和亚胺亲电子试剂都证明了分子间三组分级联反应。此外，报告了第一个阳离子 Cp*Rh(iii) 烯醇化物的 X 射线结构，其原子间距离与 η3 结合的烯醇化物一致。
Rh(iii)-catalyzed cascade addition of C–H bonds across alkene and carbonyl π-bonds to form two new σ C–C bonds is accomplished. The Rh(iii)-catalyzed cascade addition of a C–H bond across alkene and carbonyl π-bonds is reported. The reaction proceeds under mild reaction conditions with low catalyst loading. A range of directing groups were shown to be effective as was the functionalization of alkenyl in addition to aromatic C(sp2)–H bonds. When the enone and aldehyde electrophile were tethered together, cyclic β-hydroxy ketones with three contiguous stereocenters were obtained with high diastereoselectivity. The intermolecular three-component cascade reaction was demonstrated for both aldehyde and imine electrophiles. Moreover, the first X-ray structure of a cationic Cp*Rh(iii) enolate with interatomic distances consistent with an η3-bound enolate is reported.