Chemistry Department, University of Hawaii at Manoa, 2545 The Mall, Honolulu, HI 96822 (USA).
Chemistry Department, The University of Texas-Pan American, 1201 West University Drive, Edinburg, TX 78539-2999 (USA).
Angew Chem Int Ed Engl. 2015 May 18;54(21):6288-91. doi: 10.1002/anie.201500881. Epub 2015 Apr 1.
A Pd(0)-catalyzed asymmetric Nazarov-type cyclization is described. The optimized ligand for the reaction incorporates a weakly coordinating pyridine ring into a TADDOL-derived phosphoramidite (TADDOL=α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol). The reaction leads to the formation of cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers, one tertiary and one an all-carbon-atom quaternary stereocenter, in high yield and optical purity. It is noteworthy that the reaction does not require that substrates should be activated by aryl substituents.
Pd(0)催化的不对称 Nazarov 型环化反应。反应的优化配体将一个弱配位的吡啶环引入到 TADDOL 衍生的磷酰胺（TADDOL=α,α,α,α-四芳基-1,3-二恶戊环-4,5-二甲醇）中。该反应以高产率和光学纯度得到作为单一非对映异构体的环戊烯酮，其中包含两个连续的不对称中心，一个叔碳中心和一个全碳原子季碳中心。值得注意的是，该反应不需要底物通过芳基取代基活化。
