Di-tert-butyl Ethynylimidodicarbonate as a General Synthon for the β-Aminoethylation of Organic Electrophiles: Application to the Formal Synthesis of Pyrrolidinoindoline Alkaloids (±)-CPC-1 and (±)-Alline.,The Journal of Organic Chemistry

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Di-tert-butyl Ethynylimidodicarbonate as a General Synthon for the β-Aminoethylation of Organic Electrophiles: Application to the Formal Synthesis of Pyrrolidinoindoline Alkaloids (±)-CPC-1 and (±)-Alline.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-06-04 , DOI: 10.1021/acs.joc.0c00781
Ramsay E Beveridge ₁ , Yiwei Hu ₁ , Bruce Gregoire ₁ , Robert A Batey ₁

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The reagent di-tert-butyl ethynylimidodicarbonate is demonstrated as a β-aminoethyl anion synthetic equivalent. It can be used to install ethyleneamine groups by exploiting its terminal alkyne reactivity with common organic electrophiles. Reactions exemplified with this terminal ynimide reagent include additions to imines, aldehydes, ketones, pyridinium salts, Michael acceptors, epoxides, and Pd-catalyzed Sonogashira couplings. Subsequent regioselective [3 + 2] cycloadditions of the alkynyl-imides (ynimides) generate N,N-di-Boc imide-functionalized triazole and isoxazole heterocycles. Reduction of the ynimides with Pd-catalyzed hydrogenation generates ethyleneimides with easily removable N,N-di-Boc-carbamate protecting groups, allowing for a flexible ynimide-based approach to ethyleneamine installation. The utility of this two-step aminoethylation strategy was demonstrated in the short formal syntheses of pyrrolidinoindoline alkaloids (±)-CPC-1 and (±)-alline. Analogously, the reagent (N,N,N′)-tri-Boc 2-ethynylhydrazine serves as a β-hydrazinoethyl anion synthetic equivalent.

中文翻译：

乙炔基二碳酸二叔丁酯作为有机亲电子试剂的β-氨基乙基化的一般合成子：在吡咯烷基二氢吲哚啉生物碱（±）-CPC-1和（±）-碱的形式合成中的应用。

乙二胺基二碳酸二叔丁酯已证明是β-氨乙基阴离子合成的等价物。通过利用其与常见有机亲电子试剂的末端炔反应性，可用于安装亚乙基胺基。以该末端酰亚胺酰亚胺试剂为例的反应包括添加至亚胺，醛，酮，吡啶鎓盐，迈克尔受体，环氧化物和Pd催化的Sonogashira偶联。炔基酰亚胺（酰亚胺）的随后区域选择性[3 + 2]环加成反应生成N，N -N-二-Boc酰亚胺官能化的三唑和异恶唑杂环。用Pd催化的加氢还原酰亚胺可生成具有易于去除的N，N的乙二酰亚胺-di-Boc-氨基甲酸酯保护基团，允许使用基于酰亚胺的灵活方法来安装亚乙基胺。在吡咯烷二氢吲哚啉生物碱（±）-CPC-1和（±）-alline的简短形式合成中证明了这种两步氨基乙基化策略的效用。类似地，试剂（N，N，N '）-三-Boc 2-乙炔基肼用作β-肼基乙基阴离子合成当量。

更新日期：2020-07-02

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