A Facile Synthetic Approach to Nonracemic Substituted Pyrrolo-allocolchicinoids Starting from Natural Colchicine

Ekaterina S. Shchegravina; Elena V. Svirshchevskaya; Hans-Günther Schmalz; Alexey Yu Fedorov

doi:10.1055/s-0037-1610673

Synthesis, Table of Contents

Synthesis 2019; 51(07): 1611-1622
DOI: 10.1055/s-0037-1610673

paper

A Facile Synthetic Approach to Nonracemic Substituted Pyrrolo-allocolchicinoids Starting from Natural Colchicine

Ekaterina S. Shchegravina

^aDepartment of Organic Chemistry, Nizhny Novgorod State University, 23 Gagarin Avenue, 603950 Nizhny Novgorod, Russian Federation Email: afnn@rambler.ru

,

Elena V. Svirshchevskaya

^bShemyakin-Ovchinnikov Institute of Bioorganic Chemistry RAS, 16/10 Miklukho-Maklaya Street, 117997 Moscow, Russian Federation

,

Hans-Günther Schmalz

^cDepartment of Chemistry, University of Cologne, Greinstrasse 4, 50939 Cologne, Germany

,

Alexey Yu Fedorov *

^aDepartment of Organic Chemistry, Nizhny Novgorod State University, 23 Gagarin Avenue, 603950 Nizhny Novgorod, Russian Federation Email: afnn@rambler.ru

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Abstract

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Abstract

A six-step semisynthetic approach towards chiral nonracemic pyrrolo-allocolchicinoids starting from naturally occurring colchicine was developed. The synthetic scheme includes an electrocyclic tropolone ring contraction to afford allocolchicinic acid followed by the Curtius reaction, giving the corresponding aniline. The Sandmeyer reaction and copper-mediated hydrazination gave hydrazine-substituted allocolchicine. This was introduced into the Fischer indole synthesis, affording libraries of regioisomeric indole-based allocolchicine congeners.

Key words

colchicine - pyrrolo-allocolchicinoids - Fischer indole synthesis - tubulin - anti-tubulin agents

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