Cesati Richard R, de Armas Judith, Hoveyda Amir H
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
J Am Chem Soc. 2004 Jan 14;126(1):96-101. doi: 10.1021/ja0305407.
The first enantioselective synthesis of erogorgiaene (1), an inhibitor of mycobacterium tuberculosis, is disclosed. The total synthesis highlights the utility of asymmetric conjugate additions (ACA) of alkylzincs to acyclic alpha,beta-unsaturated ketones catalyzed by peptidic phosphine ligands and (CuOTf)(2).C(6)H(6). Moreover, several critical attributes of this catalytic C-C bond-forming reaction are illustrated in the context of the total synthesis; these include the significance of various structural features of the amino acid-based chiral ligands and the chiral ligand's effectiveness in reactions involving achiral and chiral substrates. In addition, the total synthesis showcases some of the special properties of nonphosphine Ru complex 3 as a highly effective catalyst for olefin cross-metathesis.
首次公开了结核分枝杆菌抑制剂埃罗戈吉烯（1）的对映选择性合成。全合成突出了肽基膦配体和（三氟甲磺酸铜）（2）·C₆H₆催化的烷基锌对无环α，β-不饱和酮的不对称共轭加成（ACA）的实用性。此外，在全合成的背景下阐述了这种催化碳-碳键形成反应的几个关键特性；这些特性包括基于氨基酸的手性配体的各种结构特征的重要性以及手性配体在涉及非手性和手性底物的反应中的有效性。此外，全合成展示了非膦钌配合物3作为烯烃交叉复分解的高效催化剂的一些特殊性质。
