Stereospecific diaza-Cope rearrangement as an efficient tool for the synthesis of DPEDA pyridine analogs and related C2-symmetric organocatalysts,Organic & Biomolecular Chemistry

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Stereospecific diaza-Cope rearrangement as an efficient tool for the synthesis of DPEDA pyridine analogs and related C2-symmetric organocatalysts
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2017-08-02 00:00:00 , DOI: 10.1039/c7ob01852e
A. S. Kucherenko _{1,

2,

3,

4} , A. A. Kostenko _{1,

2,

3,

4} , V. V. Gerasimchuk _{1,

2,

3,

4} , S. G. Zlotin _{1,

2,

3,

4}

Affiliation

A simple and efficient synthesis of enantiomerically pure (1S,2S)-1,2-di(pyridin-2-yl)- and (1R,2R)-1,2-di(pyridin-4-yl)-ethane-1,2-diamines from commercial picolinaldehyde or isonicotinaldehyde and 2,2′-((1S,2S)-1,2-diaminoethane-1,2-diyl)diphenol (HPEN) via a stereospecific diaza-Cope rearrangement has been developed. Diamine (R,R)-2b was readily converted to novel diastereomeric ionic group-supported bis-prolinamides (R,S)-1b and (R,R)-1b which appeared to be efficient organocatalysts of asymmetric cross-aldol reactions in aldehyde/aldehyde, ketone/ketone or ketone/aldehyde reagent systems under neat conditions to afford corresponding aldols in high yields and with up to 99% ee. Furthermore, catalyst (R,S)-1b could be reused over 15 times in the same or similar catalytic reactions exhibiting close to original activity and a high level of stereoinduction.

中文翻译：

立体定向_二氮杂-Cope重排可作为合成DPEDA吡啶类似物和相关C ₂对称有机催化剂的有效工具

对映体纯的（1 S，2 S）-1,2-二（吡啶-2-基）-和（1 R，2 R）-1,2-二（吡啶-4-基）的简单有效的合成-乙烷-1,2-二胺从商业吡啶甲醛或异烟醛和2,2' - （（1-小号，2小号）-1,2-二氨基乙烷-1,2-二基）联苯酚（HPEN）通过立体有择二氮杂-应对重排已开发。二胺（R，R）-2b易于转化为新型非对映体离子基团支持的双脯氨酰胺（R，S）-1b和（R，R）-图1b似乎是在纯净条件下在醛/醛，酮/酮或酮/醛试剂体系中不对称交叉醛醇缩合反应的有效有机催化剂，以高收率和高达99％的ee提供相应的醛醇缩合。此外，催化剂（R，S）-1b可在相同或相似的催化反应中重复使用超过15次，表现出接近原始的活性和高水平的立体诱导。

更新日期：2017-08-10

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