Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups

Abstract Sulfur‐containing functional groups (SFGs) are increasingly important for modern medicinal chemistry and their large structural diversity provides many opportunities for lead optimization. In an effort to simplify the access to the full set of SFGs, we report herein a versatile strategy uti...

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Main Authors: Yue Liu, Dr. Takashi Okazoe, Dr. Tim Gatzenmeier, Prof. Dr. Kyoko Nozaki
Format: Article
Language:English
Published: Wiley-VCH 2024-11-01
Series:ChemistryEurope
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Online Access:https://doi.org/10.1002/ceur.202400053
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author Yue Liu
Dr. Takashi Okazoe
Dr. Tim Gatzenmeier
Prof. Dr. Kyoko Nozaki
author_facet Yue Liu
Dr. Takashi Okazoe
Dr. Tim Gatzenmeier
Prof. Dr. Kyoko Nozaki
author_sort Yue Liu
collection DOAJ
description Abstract Sulfur‐containing functional groups (SFGs) are increasingly important for modern medicinal chemistry and their large structural diversity provides many opportunities for lead optimization. In an effort to simplify the access to the full set of SFGs, we report herein a versatile strategy utilizing (hetero)aryl trityl sulfides (ArSCPh3) as the common precursors. We developed a mild and high yielding Pd‐catalyzed thiotritylation cross‐coupling methodology to afford ArSCPh3 compounds from (hetero)aryl bromides and iodides. Efficient chemoselective derivatizations provided access to eight different SFGs and sulfur(VI) fluorine exchange (SuFEx) hubs, which open up further downstream derivatizations towards the full set of SFGs. Thereby obtainable sulfur motifs include aryl sulfur pentafluorides (ArSF5), aryl tetrafluoro‐λ6‐sulfanyl chlorides (ArSF4Cl), aryl sulfonimidoyl fluorides (ArS(O)(NR)F), aryl sulfonyl fluorides (ArSO2F), aryl sulfonic acids (ArSO3H), and aryl sulfinyl fluorides (ArSOF), which are all valuable functional groups in modern drug discovery.
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spelling doaj-art-bec70674f1e74649a1d90a28e13b25bd2024-11-12T09:17:45ZengWiley-VCHChemistryEurope2751-47652024-11-0126n/an/a10.1002/ceur.202400053Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional GroupsYue Liu0Dr. Takashi Okazoe1Dr. Tim Gatzenmeier2Prof. Dr. Kyoko Nozaki3Department of Chemistry and Biotechnology Graduate School of Engineering The University of Tokyo 2-11-16 Yayoi Bunkyo-Ku, Tokyo 113-0032 JapanDepartment of Chemistry and Biotechnology Graduate School of Engineering The University of Tokyo 2-11-16 Yayoi Bunkyo-Ku, Tokyo 113-0032 JapanDepartment of Chemistry and Biotechnology Graduate School of Engineering The University of Tokyo 2-11-16 Yayoi Bunkyo-Ku, Tokyo 113-0032 JapanDepartment of Chemistry and Biotechnology Graduate School of Engineering The University of Tokyo 2-11-16 Yayoi Bunkyo-Ku, Tokyo 113-0032 JapanAbstract Sulfur‐containing functional groups (SFGs) are increasingly important for modern medicinal chemistry and their large structural diversity provides many opportunities for lead optimization. In an effort to simplify the access to the full set of SFGs, we report herein a versatile strategy utilizing (hetero)aryl trityl sulfides (ArSCPh3) as the common precursors. We developed a mild and high yielding Pd‐catalyzed thiotritylation cross‐coupling methodology to afford ArSCPh3 compounds from (hetero)aryl bromides and iodides. Efficient chemoselective derivatizations provided access to eight different SFGs and sulfur(VI) fluorine exchange (SuFEx) hubs, which open up further downstream derivatizations towards the full set of SFGs. Thereby obtainable sulfur motifs include aryl sulfur pentafluorides (ArSF5), aryl tetrafluoro‐λ6‐sulfanyl chlorides (ArSF4Cl), aryl sulfonimidoyl fluorides (ArS(O)(NR)F), aryl sulfonyl fluorides (ArSO2F), aryl sulfonic acids (ArSO3H), and aryl sulfinyl fluorides (ArSOF), which are all valuable functional groups in modern drug discovery.https://doi.org/10.1002/ceur.202400053thiolation cross-couplingsulfur functional groupsPd catalysisSuFEx chemistrydrug derivatization
spellingShingle Yue Liu
Dr. Takashi Okazoe
Dr. Tim Gatzenmeier
Prof. Dr. Kyoko Nozaki
Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
ChemistryEurope
thiolation cross-coupling
sulfur functional groups
Pd catalysis
SuFEx chemistry
drug derivatization
title Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
title_full Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
title_fullStr Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
title_full_unstemmed Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
title_short Pd‐Catalyzed Thiotritylation Cross‐Coupling of Aryl Bromides and Iodides to Access Sulfur Functional Groups
title_sort pd catalyzed thiotritylation cross coupling of aryl bromides and iodides to access sulfur functional groups
topic thiolation cross-coupling
sulfur functional groups
Pd catalysis
SuFEx chemistry
drug derivatization
url https://doi.org/10.1002/ceur.202400053
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AT drtimgatzenmeier pdcatalyzedthiotritylationcrosscouplingofarylbromidesandiodidestoaccesssulfurfunctionalgroups
AT profdrkyokonozaki pdcatalyzedthiotritylationcrosscouplingofarylbromidesandiodidestoaccesssulfurfunctionalgroups