The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Org Lett. 2017 Apr 7;19(7):1698-1701. doi: 10.1021/acs.orglett.7b00418. Epub 2017 Mar 28.
The first enantioselective total synthesis of the epipolythiodiketopiperazine (ETP) natural product (-)-acetylapoaranotin (3) is reported. The concise synthesis was enabled by an eight-step synthesis of a key cyclohexadienol-containing amino ester building block. The absolute stereochemistry of both amino ester building blocks used in the synthesis is set through catalytic asymmetric (1,3)-dipolar cycloaddition reactions. The formal syntheses of (-)-emethallicin E and (-)-haemotocin are also achieved through the preparation of a symmetric cyclohexadienol-containing diketopiperazine.
首次报道了手性硫杂二酮哌嗪（ETP）天然产物（-）-乙酰阿泊拉烷毒素（3）的对映选择性全合成。通过八步合成关键的含环己二烯醇的氨基酯砌块，实现了简洁的合成。通过催化不对称（1,3）-偶极环加成反应，确定了用于合成的两个氨基酯砌块的绝对立体化学。通过制备含有对称环己二烯醇的二酮哌嗪，还实现了（-）-埃美他西林 E 和（-）-血红素毒素的形式合成。
