A General Route to 3-Thiosubstituted Steroids via Copper-Catalyzed C–S Coupling

Mikhail J. Parulava; Yury N. Kotovshchikov; Gennadij V. Latyshev; Darina V. Sokolova; Nikolay V. Lukashev; Irina P. Beletskaya

doi:10.1055/a-2520-0317

Synthesis, Table of Contents

Synthesis 2025; 57(08): 1481-1489
DOI: 10.1055/a-2520-0317

paper

A General Route to 3-Thiosubstituted Steroids via Copper-Catalyzed C–S Coupling

Mikhail J. Parulava

^aChemistry Department, M. V. Lomonosov Moscow State University, 1/3 Leninskiye Gory, Moscow 119991, Russian Federation

,

Yury N. Kotovshchikov ∗

^aChemistry Department, M. V. Lomonosov Moscow State University, 1/3 Leninskiye Gory, Moscow 119991, Russian Federation

,

Gennadij V. Latyshev∗

^aChemistry Department, M. V. Lomonosov Moscow State University, 1/3 Leninskiye Gory, Moscow 119991, Russian Federation

,

Darina V. Sokolova

^bRUDN University, 6 Miklukho-Maklaya str., Moscow 117198, Russian Federation

^cN. N. Blokhin National Medical Research Center of Oncology of the Ministry of Health of Russia, 24 Kashirskoe Shosse, Moscow 115478, Russian Federation

,

Nikolay V. Lukashev

^aChemistry Department, M. V. Lomonosov Moscow State University, 1/3 Leninskiye Gory, Moscow 119991, Russian Federation

,

Irina P. Beletskaya

^aChemistry Department, M. V. Lomonosov Moscow State University, 1/3 Leninskiye Gory, Moscow 119991, Russian Federation

› Author Affiliations

Abstract

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Abstract

A convenient and efficient approach to 3-thiosubstituted androstanes has been developed. The formation of a C(sp²)–S bond was achieved through the Cu-catalyzed coupling of steroidal iododienes with a variety of S-nucleophiles, such as (het)aryl thiols and dithiocarbamates. A simple catalytic system comprising CuI without auxiliary ligands enabled the preparation of a library of target compounds in good to high yields. A moderate inhibitory activity against hormone-dependent cancer cell lines was demonstrated for representative 3-thiolated steroids.

Key words

copper - catalysis - steroids - thiols - dithiocarbamates - heterocycles

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