Rh_2(OCOCF_3)_4试剂在仲醇和叔醇类结构绝对构型确定中的应用

Application of dirhodium reagent Rh_2(OCOCF_3)_4 to the determination of the absolute configurations of secondary and tertiary alcohols

天然产物绝对构型的确定是一个令人关注的研究领域。与化合物手性中心直接相关的圆二色(circular dichroism,CD)谱法是确定溶液中手性化合物绝对构型的有效手段之一。国外文献介绍了一种通过使用过渡金属试剂Rh2(OCOCF3)4进行手性仲醇或叔醇结构绝对构型的确定方法,手性仲醇或叔醇与Rh2(OCOCF3)4络合后,其CD图谱在600~270 nm范围内有A^F 6个吸收带,其中出现在350 nm处的E带可通过bulkiness规则来确定仲醇或叔醇的绝对构型。本文将对Rh2(OCOCF3)4作为辅助生色团诱导CD,确定天然产物手性仲醇或叔醇结构绝对构型的研究进行系统介绍。

The determination of the absolute configuration of natural products has drawn great attention for a long time. The circular dichroism（CD） spectroscopy appears to be an efficient method for determining the absolute configuration of chiral compounds in solution. Studies from abroad indicated a straightforward method which employed a transition metal chelate dirhodium reagent Rh2（OCOCF3）4for the assignment of the absolute configurations of the secondary and tertiary alcohols. The CD spectra of the in situ complexes of chiral alcohols with Rh2（OCOCF3）4showed up to 6 Cotton effects（A-F）at the range of 600-270 nm.It was demonstrated that the E band,appearing at ca. 350 nm,can be used for correlation of its sign and the stereochemistry of the secondary or tertiary alcohols,by applying the bulkiness rule. In this review,the methodology including theory,procedures and results,as well as the application examples are presented.