Synthesis, characterization, and copper(II) chelates of 1,11-dithia-4,8-diazacyclotetradecane

Ian S. Taschner; Tia L. Walker; Hunter S. Dehaan; Briana R. Schrage; Christopher J. Ziegler; Michael J. Taschner

doi:10.1021/acs.joc.9b01682

Synthesis, characterization, and copper(II) chelates of 1,11-dithia-4,8-diazacyclotetradecane

Ian S. Taschner, Tia L. Walker, Hunter S. Dehaan, Briana R. Schrage, Christopher J. Ziegler, Michael J. Taschner

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Synthesis of 1,11-dithia-4,8-diazacyclotetradecane (L1), a constitutional isomer of the macrocyclic [14]aneN₂S₂ series, is accompanied with reaction and method optimization. Chelation of L1 with copper(II) provided assessment of lattice packing, ring contortion, and evidence of conformational fluxionality in solution through two unique crystal structures: L1Cu(ClO4)₂ and [(L1Cu)₂μ-Cl](ClO₄)₃. Multiple synthetic approaches are presented, supplemented with reaction methodology and reagent screening to access [14]aneN₂S₂ L1. Reductive alkylation of bis-tosyl-cystamine was integrated into the synthetic route, eliminating the use and isolation of volatile thiols and streamlining the synthetic scale-up. Late-stage cleavage of protecting sulfonamides was addressed using reductive N-S cleavage to furnish macrocyclic freebase L1.

Original language	English
Pages (from-to)	11091-11102
Number of pages	12
Journal	Journal of Organic Chemistry
Volume	84
Issue number	17
DOIs	https://doi.org/10.1021/acs.joc.9b01682
State	Published - Sep 6 2019
Externally published	Yes

Funding

The authors thank the Ohio Board of Regents for funds used to purchase the Bruker-Nonius Apex CCDC X-ray diffractometer and the National Science Foundation (CHE-0840446). The authors thank the University of Notre Dame Mass Spectrometry and Proteomics Facility, supported by NSF grant CHE-0741793, for exact mass measurements on compound 2 and Indiana University Bloomington Mass Spectrometry Facility for exact mass measurements on all additional compounds. This work was also supported by NIH 1R15 GM119074-01.

Funders	Funder number
Indiana University Bloomington Mass Spectrometry Facility
University of Notre Dame Mass Spectrometry and Proteomics Facility
National Science Foundation	CHE-0741793, CHE-0840446
National Institutes of Health
National Institute of General Medical Sciences	R15GM119074
Ohio Board of Regents

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title = "Synthesis, characterization, and copper(II) chelates of 1,11-dithia-4,8-diazacyclotetradecane",

abstract = "Synthesis of 1,11-dithia-4,8-diazacyclotetradecane (L1), a constitutional isomer of the macrocyclic [14]aneN2S2 series, is accompanied with reaction and method optimization. Chelation of L1 with copper(II) provided assessment of lattice packing, ring contortion, and evidence of conformational fluxionality in solution through two unique crystal structures: L1Cu(ClO4)2 and [(L1Cu)2μ-Cl](ClO4)3. Multiple synthetic approaches are presented, supplemented with reaction methodology and reagent screening to access [14]aneN2S2 L1. Reductive alkylation of bis-tosyl-cystamine was integrated into the synthetic route, eliminating the use and isolation of volatile thiols and streamlining the synthetic scale-up. Late-stage cleavage of protecting sulfonamides was addressed using reductive N-S cleavage to furnish macrocyclic freebase L1.",

author = "Taschner, {Ian S.} and Walker, {Tia L.} and Dehaan, {Hunter S.} and Schrage, {Briana R.} and Ziegler, {Christopher J.} and Taschner, {Michael J.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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doi = "10.1021/acs.joc.9b01682",

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T1 - Synthesis, characterization, and copper(II) chelates of 1,11-dithia-4,8-diazacyclotetradecane

AU - Taschner, Ian S.

AU - Walker, Tia L.

AU - Dehaan, Hunter S.

AU - Schrage, Briana R.

AU - Ziegler, Christopher J.

AU - Taschner, Michael J.

PY - 2019/9/6

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N2 - Synthesis of 1,11-dithia-4,8-diazacyclotetradecane (L1), a constitutional isomer of the macrocyclic [14]aneN2S2 series, is accompanied with reaction and method optimization. Chelation of L1 with copper(II) provided assessment of lattice packing, ring contortion, and evidence of conformational fluxionality in solution through two unique crystal structures: L1Cu(ClO4)2 and [(L1Cu)2μ-Cl](ClO4)3. Multiple synthetic approaches are presented, supplemented with reaction methodology and reagent screening to access [14]aneN2S2 L1. Reductive alkylation of bis-tosyl-cystamine was integrated into the synthetic route, eliminating the use and isolation of volatile thiols and streamlining the synthetic scale-up. Late-stage cleavage of protecting sulfonamides was addressed using reductive N-S cleavage to furnish macrocyclic freebase L1.

AB - Synthesis of 1,11-dithia-4,8-diazacyclotetradecane (L1), a constitutional isomer of the macrocyclic [14]aneN2S2 series, is accompanied with reaction and method optimization. Chelation of L1 with copper(II) provided assessment of lattice packing, ring contortion, and evidence of conformational fluxionality in solution through two unique crystal structures: L1Cu(ClO4)2 and [(L1Cu)2μ-Cl](ClO4)3. Multiple synthetic approaches are presented, supplemented with reaction methodology and reagent screening to access [14]aneN2S2 L1. Reductive alkylation of bis-tosyl-cystamine was integrated into the synthetic route, eliminating the use and isolation of volatile thiols and streamlining the synthetic scale-up. Late-stage cleavage of protecting sulfonamides was addressed using reductive N-S cleavage to furnish macrocyclic freebase L1.

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JF - Journal of Organic Chemistry

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Synthesis, characterization, and copper(II) chelates of 1,11-dithia-4,8-diazacyclotetradecane

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