Sun Chunrui, Lee Hyunjin, Lee Daesung
Department of Chemistry, University of Illinois at Chicago , 845 West Taylor Street, Chicago, Illinois 60607, United States.
Org Lett. 2015 Nov 6;17(21):5348-51. doi: 10.1021/acs.orglett.5b02709. Epub 2015 Oct 26.
The carbocyclic core of massadine has been synthesized relying on a stereoselective formal [3 + 2] cycloaddition of lithiumtrimethylsilyldiazomethane with α,β-unsaturated esters to form a Δ(2)-pyrazoline moiety followed by facile N-N bond cleavage. A unique feature of the current approach is the direct installation of the tertiary α-amino center and a β-cyano group in a cis arrangement on the resulting cyclopentane framework via a previously developed formal aminocyanation protocol.
依靠三甲基硅基重氮甲烷锂与α,β-不饱和酯的立体选择性形式[3 + 2]环加成反应，形成Δ(2)-吡唑啉部分，随后进行简便的N-N键裂解。当前方法的一个独特之处在于，通过先前开发的形式氨基氰化方案，在所得环戊烷骨架上以顺式排列直接安装叔α-氨基中心和β-氰基。
