A novel heterocyclic atom exchange reaction with Lawesson's reagent: a one-pot synthesis of dithiomaltol

Brayton, Daniel F.; Jacobsen, Faith E.; Cohen, Seth M.; Farmer, Patrick J.

doi:10.1039/b511966a

Cited by 28 publications

(13 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To obtain the requisite 3HPT compound 10a , the O -methyl protected 3HP 7a was first converted to its thione analog 9 using Lawesson’s reagent. 14 Subsequent BBr 3 deprotection of the methyl ether group yielded the desired compound 10a (Scheme 1). …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure–Activity Relationship of 3-Hydroxypyridine-2-thione-Based Histone Deacetylase Inhibitors

Sodji¹,

Patil²,

Kornacki

et al. 2013

J. Med. Chem.

View full text Add to dashboard Cite

We have previously identified 3-hydroxypyridin-2-thione (3HPT) as a novel zinc binding group for histone deacetylase (HDAC) inhibition. Early structure activity relationship (SAR) studies led to various small molecules possessing selective inhibitory activity against HDAC6 or HDAC8 but are devoid of HDAC1 inhibition. To further delineate the depth of the SAR of 3HPT-derived HDAC inhibitors (HDACi), we have extended the SAR studies to include the linker region and the surface recognition group to optimize the HDAC inhibition. The current efforts resulted in the identification of two lead compounds 10d and 14e with potent HDAC6 and HDAC8 activities, but that are inactive against HDAC1. These new HDACi possess anti-cancer activities against various cancer cell lines including Jurkat J-γ1 against which SAHA and the previously disclosed 3HPT-derived HDACi were inactive.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure–Activity Relationship of 3-Hydroxypyridine-2-thione-Based Histone Deacetylase Inhibitors

Sodji¹,

Patil²,

Kornacki

et al. 2013

J. Med. Chem.

View full text Add to dashboard Cite

show abstract

“…The conversion of 3-hydroxy-4-pyr(id)ones to the corresponding thionated compounds may be achieved using different strategies and the most common are (i) the addition of 1 eq Lawesson's reagent [49] and (ii) the reaction with an excess of P 4 S 10 [50] under various conditions [51]. The reaction of two equivalents of Lawesson's reagent with 4-pyrones was reported to lead to the formation of dithiopyrones [52].…”

Section: Thio-and Selenopyr(id)onesmentioning

confidence: 99%

Pyrone derivatives and metals: From natural products to metal-based drugs

Kandioller

Kurzwernhart

Hanif

et al. 2011

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…17,18 A ring substituted derivative, 3-hydroxy-2-methyl-4H-thiopyran-4-thione, dithiomaltol or Httma, was first reported by Brayton, and displayed unusual aromaticity characterized by a downfield shift in the vinylic proton peaks in the 1 H NMR. 19 Recently we reported that the bis-bipyridyl Ru complex of dithiomaltol, [Ru(bpy) 2 (ttma)][PF 6 ] or 1, undergoes C-H activation at a pendant alkyl position upon electrochemical or bulk oxidation, yielding [Ru(bpy) 2 (ttma-alcohol)] + 2 and [Ru(bpy) 2 (ttma-aldehyde)] + 3 as products, Scheme 1. 20 In this report we examine the photo-initiation of similar oxidative reactivity for compound 1 and the homoleptic Zn(ttma) 2 complex, 4, using flash quench methodology, 21 employing electron acceptors 4,4′-dimethyl-1,1′-trimethylene-2,2′dipyridinium (DTDP 2+ ), 1,1′-dimethyl-4,4′-bipyridinium (MV 2+ ), Co(NH 3 ) 5 Cl 2+ , Ru(NH 3 ) 6 3+ , and 2,3-dichloro-5,6-dicyano-1,4benzoquinone (DDQ), Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

Ligand-based photooxidations of dithiomaltolato complexes of Ru(ii) and Zn(ii): photolytic CH activation and evidence of singlet oxygen generation and quenching

et al. 2014

Self Cite

View full text Add to dashboard Cite

The complex [Ru(bpy)2(ttma)](+) (bpy = 2,2'-bipyridine; ttma = 3-hydroxy-2-methyl-thiopyran-4-thionate, 1, has previously been shown to undergo an unusual C-H activation of the dithiomaltolato ligand upon outer-sphere oxidation. The reaction generated alcohol and aldehyde products 2 and 3 from C-H oxidation of the pendant methyl group. In this report, we demonstrate that the same products are formed upon photolysis of 1 in presence of mild oxidants such as methyl viologen, [Ru(NH3)6](3+) and [Co(NH3)5Cl](2+), which do not oxidize 1 in the dark. This reactivity is engendered only upon excitation into an absorption band attributed to the ttma ligand. Analogous experiments with the homoleptic Zn(ttma)2, 4, also result in reduction of electron acceptors upon excitation of the ttma absorption band. Complexes 1 and 4 exhibit short-lived visible fluorescence and long-lived near-infrared phosphorescence bands. Singlet oxygen is both generated and quenched during aerobic excitation of 1 or 4, but is not involved in the C-H activation process.

show abstract

A novel heterocyclic atom exchange reaction with Lawesson's reagent: a one-pot synthesis of dithiomaltol

Abstract: A one-pot reaction of maltol with Lawesson's reagent generates dithiomaltol, a thiopyran-4-thione, via an unusual heterocyclic atom exchange (HCAE) reaction; only pyrones with proton or aliphatic substituents undergo the HCAE substitution.

Cited by 28 publications

References 23 publications

Synthesis and Structure–Activity Relationship of 3-Hydroxypyridine-2-thione-Based Histone Deacetylase Inhibitors

Synthesis and Structure–Activity Relationship of 3-Hydroxypyridine-2-thione-Based Histone Deacetylase Inhibitors

Pyrone derivatives and metals: From natural products to metal-based drugs

Ligand-based photooxidations of dithiomaltolato complexes of Ru(ii) and Zn(ii): photolytic CH activation and evidence of singlet oxygen generation and quenching

Contact Info

Product

Resources

About