Catalytic Asymmetric Synthesis of the endo-6-Aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one Natural Product from Ligusticum Chuanxing via 1,3-Dipolar Cycloaddition of a Formyl-Derived Carbonyl Ylide Using Rh_2(S-TCPTTL)_4
Catalytic Asymmetric Synthesis of the endo-6-Aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one Natural Product from Ligusticum Chuanxing via 1,3-Dipolar Cycloaddition of a Formyl-Derived Carbonyl Ylide Using Rh_2(S-TCPTTL)_4
复制标题
使用Rh_2（通过甲酰基衍生的羰基叶立德的1,3-偶极环加成反应从川杏中催化不对称合成内-6-芳基-8-氧杂二环[3.2.1]oct-3-en-2-one天然产物
作者：
Shimada;N.; Hanari;T.; Kurosaki;Y.; Takeda;K.; Anada;M.; Nambu;H.; Shiro;M.; Hashimoto;S.
本文研究了α-重氮-β-酮酯衍生的六元环甲酰基羰基叶立德与苯乙炔衍生物在四[N-四氯邻苯二甲酰-（S）-叔亮氨酸]铑（Ⅱ）催化下的反应（S-TCPTTL）4提供了含有高达97%ee的8-氧杂双环[3.2.1]辛烷环体系的环加合物。这代表了对映选择性1，环状甲酰基羰基叶立德的3-偶极环加成。利用该催化方法，实现了从川杏霍特中不对称合成内-6-芳基-8-氧杂双环[3.2.1]辛-3-烯-2-酮天然产物1。
The reaction of a six-membered cyclic formyl-carbonyl ylide derived from α-diazo-β-ketoester with phenylacetylene derivatives under the catalysis of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides cycloadducts containing an 8-oxabicyclo[3.2.1]octane ring system in up to 97% ee. This represents the first example of an enantioselective 1,3-dipolar cycloaddition of a cyclic formyl-carbonyl ylide. Using this catalytic process, an asymmetric synthesis ofendo-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural product1fromLigusticum chuanxing Hort.has been achieved.