Facile Ring‐Expansion Substitution Reactions of 1,3‐Dithiolanes and 1,3‐Dithianes Initiated by Electrophilic Reagents to Produce Monohalo‐, ‐cyano‐, ‐azido‐ and ‐thiocyanato‐1,4‐dithiins and ‐1,4‐dithiepins

Firouzabadi, Habib; Iranpoor, Nasser; Garzan, Atefeh; Shaterian, Hamid Reza; Ebrahimzadeh, Farzaneh

doi:10.1002/ejoc.200400502

Cited by 21 publications

(5 citation statements)

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“…NBu n 4 N 3 was prepared as described elsewhere. 31 Warning! Azide and perchlorate salts are potentially explosiVe; such compounds should be synthesized and used in small quantities and treated with utmost care at all times.…”

Section: Methodsmentioning

confidence: 99%

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Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters

et al. 2008

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Syntheses, crystal structures, and magnetochemical characterization are reported for the three new nickel(II) clusters [Ni(14)(OH)(4)(N(3))(8)(pao)(14)(paoH)(2)(H(2)O)(2)](ClO(4))(2) (1), [Ni(12)Na(2)(OH)(4)(N(3))(8)(pao)(12)(H(2)O)(10)](OH)(2) (2), and [Ni(5)(ppko)(5)(H(2)O)(7)](NO(3))(5) (3) (paoH = pyridine-2-carbaldehyde oxime, ppkoH = di-2-pyridyl ketone oxime). The reaction of Ni(ClO(4))(2).6H(2)O with paoH and NBu(n)(4)N(3) in H(2)O/MeCN in the presence of NEt(3), gave 1 in 65% yield. Complex 2 was obtained in 60% yield from the reaction of NiCl(2).6H(2)O with paoH and NaN(3) in H(2)O/MeCN in the presence of NaOH. The reaction of Ni(NO(3))(2).6H(2)O with ppkoH in EtOH in the presence of LiOH afforded complex 3 in 75% yield. The complexes all contain novel core topologies. The core of 1 comprises a central Ni(4) rhombus between two Ni(5). Complex 1 is the largest metal/oxime cluster discovered to date, as well as the first Ni(II)(14) coordination complex and the largest Ni(II)/N(3)(-) cluster. Complex 2 has a Ni(12)Na(2) topology that is very similar to that of 1, but with two central Ni(II) atoms of 1 replaced with Na(I) atoms. The core of 3 consists of four Ni(II) atoms forming a highly distorted tetrahedron, with the fifth Ni(II) atom lying almost on one of the edges. Variable-temperature, solid-state dc susceptibility and magnetization studies were carried out on complexes 1-3, and these were complemented with ac susceptibility data for 1 and 2. Fitting of the obtained M/(Nmu(B)) vs H/T data by matrix diagonalization and including axial zero-field splitting (D) gave ground-state spin (S) and D values of S = 6, D = -0.12(3) cm(-1) for 1 and S = 3, D = -0.20(5) cm(-1) for each of the two essentially noninteracting S = 3 Ni(6) subunits of 2. The data for 3 indicate antiferromagnetic exchange interactions and an S = 1 ground state. A simple 2-J model was found to be adequate to describe the variable-temperature dc susceptibility data. The combined work demonstrates the ligating flexibility of pao(-) and ppko(-), and their usefulness in the synthesis of polynuclear Ni(x) clusters with or without the presence of ancillary ligands.

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Section: Methodsmentioning

confidence: 99%

“…All manipulations were performed under aerobic conditions using reagents and solvents as received. NBu n 4 N 3 was prepared as described elsewhere …”

Section: Methodsmentioning

confidence: 99%

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters

et al. 2008

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“…Generated from N-bromosuccinimide (NBS) and ammonium thiocyanate, N-thiocyanatosuccinimide was used as an electrophilic reagent in the ring-expansion substitution reactions of 1,3-dithiolanes and 1,3-dithianes (Scheme 19). 22 Various 2-aryl-3-thiocyanato 1,4-dithiins and 1,4-dithiepins have been obtained in good yields by this method. II.B.…”

Section: Synthesis Of Thiocyanatesmentioning

confidence: 98%

Recent advances in the chemistry of organic thiocyanates

et al. 2016

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Organic thiocyanates are important synthetic intermediates to access valuable sulfur-containing compounds. In this review the different methods for their preparation and their synthetic applications will be presented. The literature of the last 15 years will be covered, highlighting selected recent advances in the chemistry of this class of compounds. We hope to offer chemists the tools to have a good grasp of this singular functionality and open the door to further progress in this chemistry.

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“…[1d,m] In the year 2020, Cai and coworkers successfully devised an electrochemical deborylative thiocyanation reaction of phenyl boronic acids to produce analogous phenylthiocyanates with good functional group tolerance with trimethylsilylisothiocyanate (TMSNCS) as a thiocyanation reagent under ambient conditions. [19b] At present, electrophilic substitution reactions represent a viable and innovative approach for incorporating SCN groups into diverse compounds through the interaction of the electron-rich system with newly developed organic electrophilic thiocyanation reagents, [1d,g] including N-thiocyanatosuccinimide (NTS), [13] N-thiocyanatosaccharin (NTSc), [14] N-thiocyanatophthalimide (NTP), [15] N-thiocyanatodibenzenesulfonimide (NTSI), [16] thiocyanobenziodoxolone (Bl-SCN) [17] . In recent years, noteworthy advancement has been made towards the effective incorporation of CN groups into molecules through the use of alternative inorganic metal cyano sources.…”

Section: R E V I E W T H E C H E M I C a L R E C O R Dmentioning

confidence: 99%

“…The author also highlighted various applications of sulfoxide (10) into different substituents in a one-pot approach that were transformed in decent yields into thioalkyne (12) in 80 % isolated yield by screening with the addition of a solution of lithium alkynylide in THF. Besides, when Ruppert's reagent (TMSCF 3 ) and TBAF were utilized, trifluoromethyl sulfide (13) in one pot was produced in a 49 % yield. Correspondingly, the reaction of thiocyanate (11) with a combination of hydrogen peroxide and trifluoroacetic anhydride (TFAA) in dichloromethane by an oxidation protocol yielded the corresponding sulfonyl cyanide ( 14) in a good to moderate yield (Scheme 7).…”

Section: Indirect Thiocyanation Of Sulfoxide Derivatives Using Tmscn ...mentioning

confidence: 99%

Recent Advancement on the Indirect or Combined Alternative Thiocyanate Sources for the Construction of S−CN Bonds

Karmaker,

Yang

2023

The Chemical Record

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The process of thiocyanation is a notable chemical conversion owing to the extensive range of applications associated with thiocyanate compounds in the field of organic chemistry. In past centuries, the thiocyanation reaction incorporated metal thiocyanates or thiocyanate salts as sources of thiocyanate, which are environmentally detrimental and undesirable. In recent literature, there have been numerous instances where combined or indirect alternative sources of thiocyanate have been employed as agents for thiocyanation, showcasing their noteworthy applications. The present literature review focuses on elucidating the ramifications associated with the utilization of indirect or combined alternative sources of thiocyanate in various thiocyanation reactions.

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Facile Ring‐Expansion Substitution Reactions of 1,3‐Dithiolanes and 1,3‐Dithianes Initiated by Electrophilic Reagents to Produce Monohalo‐, ‐cyano‐, ‐azido‐ and ‐thiocyanato‐1,4‐dithiins and ‐1,4‐dithiepins

Cited by 21 publications

References 16 publications

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters

Recent advances in the chemistry of organic thiocyanates

Recent Advancement on the Indirect or Combined Alternative Thiocyanate Sources for the Construction of S−CN Bonds

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Facile Ring‐Expansion Substitution Reactions of 1,3‐Dithiolanes and 1,3‐Dithianes Initiated by Electrophilic Reagents to Produce Monohalo‐, ‐cyano‐, ‐azido‐ and ‐thiocyanato‐1,4‐dithiins and ‐1,4‐dithiepins

Cited by 21 publications

References 16 publications

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni5, Ni12Na2, and Ni14 Clusters

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni5, Ni12Na2, and Ni14 Clusters

Recent advances in the chemistry of organic thiocyanates

Recent Advancement on the Indirect or Combined Alternative Thiocyanate Sources for the Construction of S−CN Bonds

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Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters

Unusual Structural Types in Nickel Cluster Chemistry from the Use of Pyridyl Oximes: Ni₅, Ni₁₂Na₂, and Ni₁₄ Clusters