Molander Gary A, Dehmel Florian
Contribution from the Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA.
J Am Chem Soc. 2004 Aug 25;126(33):10313-8. doi: 10.1021/ja047190o.
A formal total synthesis of oximidine II has been achieved, employing a Suzuki-type coupling approach to construct the highly strained, polyunsaturated 12-membered macrolactone. To achieve this goal, benefit was derived from the stability of potassium alkenyltrifluoroborates to establish conditions for the macrocyclization. The stereocontrolled formation of the cis-1,2-diol subunit was accomplished using a diastereoselective, reagent controlled addition to a chiral aldehyde utilizing the Carreira protocol. Advantage was taken of the Snieckus hydroborating reagent to gain access to the key trifluoroborate needed for the macrocyclization.
已实现了奥昔米定II的形式全合成，采用铃木型偶联方法构建高度应变的多不饱和12元大环内酯。为实现这一目标，利用链烯基三氟硼酸钾的稳定性来确定大环化的条件。顺式-1,2-二醇亚基的立体控制形成是通过使用Carreira方法，将非对映选择性、试剂控制的加成反应应用于手性醛来完成的。利用Snieckus硼氢化试剂获得大环化所需的关键三氟硼酸盐。
