Semakul Natthawat, Jackson Kelvin E, Paton Robert S, Rovis Tomislav
Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , USA.
Chemistry Research Laboratory , University of Oxford , Mansfield Road , Oxford OX1 3TA , UK . Email:
Chem Sci. 2017 Feb 1;8(2):1015-1020. doi: 10.1039/c6sc02587k. Epub 2016 Sep 23.
The diastereoselective coupling of -substituted arylhydroxamates and cyclopropenes mediated by Rh(iii) catalysis was successfully developed. Through ligand development, the diastereoselectivity of this reaction was improved using a heptamethylindenyl (Ind*) ligand, which has been rationalized using quantum chemical calculations. In addition, the nature of the -substituted ester of benzhydroxamic acid proved important for high diastereoselectivity. This transformation tolerates a variety of benzamides and cyclopropenes that furnish cyclopropa[]dihydroisoquinolones with high diastereocontrol, which could then be easily transformed into synthetically useful building blocks for pharmaceuticals and bio-active molecules.
成功开发了由铑（III）催化介导的α-取代芳基异羟肟酸酯与环丙烯的非对映选择性偶联反应。通过配体开发，使用七甲基茚基（Ind*）配体提高了该反应的非对映选择性，这已通过量子化学计算得到合理解释。此外，苯甲异羟肟酸的α-取代酯的性质被证明对高非对映选择性很重要。这种转化能够耐受多种苯甲酰胺和环丙烯，它们能以高非对映选择性提供环丙[a]二氢异喹啉酮，然后可以很容易地转化为用于药物和生物活性分子的合成有用的结构单元。
