Green asymmetric synthesis of Warfarin and Coumachlor in pure water catalyzed by quinoline-derived 1,2-diamines,Green Chemistry

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Green asymmetric synthesis of Warfarin and Coumachlor in pure water catalyzed by quinoline-derived 1,2-diamines
Green Chemistry ( IF 9.3 ) Pub Date : 2018-01-03 00:00:00 , DOI: 10.1039/c7gc03626d
Alexander S. Kucherenko _{1,

2,

3,

4} , Alexey A. Kostenko _{1,

2,

3,

4} , Galina M. Zhdankina _{1,

2,

3,

4} , Olga Yu. Kuznetsova _{1,

2,

3,

4} , Sergei G. Zlotin _{1,

2,

3,

4}

Affiliation

Simple enantiomerically pure C₂-symmetric quinoline (isoquinoline)-derived 1,2-diamines were synthesized from the corresponding aldehydes via stereospecific diaza-Cope rearrangement with 2,2′-(1,2-diaminoethane-1,2-diyl)diphenol (HPEN). Efficient green synthesis of both enantiomers of the anticoagulant Warfarin and rodenticide Coumachlor was achieved in an aqueous medium via the asymmetric iminium-type Michael reaction in the presence of the catalysts 8e and (ent)-8e in combination with (R)- or (S)-mandelic acid, respectively. This procedure provides high enantioselectivity (up to 91% ee), which has never been attained for these bioactive compounds with the known catalysts under aqueous conditions. Nearly optically pure Warfarin (∼99% ee) was prepared via a green isolation procedure, which included acidic precipitation of the crude product from a basic aqueous solution followed by single recrystallization. Furthermore, unlike the known primary amine-derived organocatalysts, the developed aqueous catalytic system does not produce parasitic byproducts and can be recovered and reused in the asymmetric reaction.

中文翻译：

喹啉衍生的1,2-二胺催化纯净水中绿色的不对称合成华法林和香豆酚

通过2,2'-（1,2-（1,2-二氨基乙烷-1,2-二基）二酚）的立体定向二氮杂-Cope重排，由相应的醛合成简单的对映体纯的C ₂对称喹啉（异喹啉）衍生的1,2-二胺（HPEN）。抗凝血剂华法林和灭鼠剂Coumachlor的两种对映体的高效的绿色合成在水性介质中实现经在催化剂的存在下，非对称亚铵型迈克尔反应器8e和（ENT - ）8E与（组合[R ）-或（小号）-扁桃酸。该方法提供了高对映选择性（高达91％ee），对于这些生物活性化合物，用已知的催化剂在水性条件下从未达到过。通过绿色分离步骤制备了几乎光学纯的华法林（〜99％ee），包括从碱性水溶液中酸性沉淀出粗产物，然后进行单次重结晶。此外，与已知的伯胺衍生的有机催化剂不同，所开发的水性催化体系不产生寄生副产物，并且可以被回收并重新用于不对称反应中。

更新日期：2018-02-06

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