Synthetic Utility of Umpoled Diaryl Thioketone−Lanthanoid Intermediates:  Desulfurization, Cross Coupling with Electrophiles, and Desulfurizative Homocoupling

Makioka, Yoshikazu; Uebori, S.; Tsuno, Masumi; Taniguchi, Yoshihiro; Takaki, Ken; Fujiwara, Yoshiyuki

doi:10.1021/jo951355h

Cited by 26 publications

(9 citation statements)

References 30 publications

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“…Melting point determinations and (or) gas chromatography (GC) were used to establish purity. All melting points and 1 H and 13 C NMR (Bruker 250 MHz using CDCl 3 as the solvent) matched literature values (49,50).…”

Section: Methodssupporting

confidence: 72%

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Shea¹,

Schepp²,

Keirstead³

et al. 2005

Can. J. Chem.

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The oxidation of diarylmethanes is a multistep process involving initial formation of a radical cation, deprotonation of the radical cation to the radical, and oxidation of the radical to the carbocation. The dynamics and efficiency of the last two steps in this process, namely deprotonation and oxidation, in acidic zeolites and non-acid zeolites are examined in the present work as a function of the acidity of the diarylmethane radical cations and the oxidation potential of the diarylmethyl radicals. Our results indicate that rate constants for deprotonation strongly depend on the acidity of the radical cations, but not on the composition of the zeolites. In addition, oxidation of the radicals to the diarylmethyl cations is strongly dependent on both the oxidation potential of the radicals and the oxidizing ability of the zeolite. This dependence allows oxidation potentials of the zeolites to be estimated.Résumé : L'oxydation de diarylméthanes est un processus en plusieurs étapes qui implique la formation initiale d'un cation radical, une déprotonation du cation radical et une oxydation du radical en carbocation. On a étudié la dynamique et l'efficacité des deux dernières étapes de ce processus, soit la déprotonation et l'oxydation, dans des zéolites acides et des zéolites non acides, en fonction de l'acidité des cations radicaux diarylméthanes et du potentiel d'oxydation des radicaux diarylméthyles. Les résultats obtenus indiquent que les constantes de vitesse pour la déproto-nation dépendent fortement de l'acidité des cations radicaux, mais pas sur la composition des zéolites. De plus, l'oxydation des radicaux en cations diarylméthyles est fortement dépendante à la fois sur le potentiel d'oxydation des radicaux et sur l'habilité des zéolites à oxyder. Cette dépendance permet d'évaluer les potentiels d'oxydation des zéo-lites.

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Section: Methodssupporting

confidence: 72%

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Shea¹,

Schepp²,

Keirstead³

et al. 2005

Can. J. Chem.

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“…Alkylation of the six-membered thiazine thione ring is known to take place at the thione sulfur atom. It is therefore not surprising to see the formation of 5a from 3a or from 2a in CH 2 Cl 2 .…”

Section: Resultsmentioning

confidence: 99%

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane

et al. 2003

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Treatment of the ruthenium acetylide complexes [M]C⋮CPh (1a, [M] = [Ru] = Cp(Ph2PCH2CH2PPh2)Ru; 1b, [M] = [Ru‘] = Cp(PPh3)[P(OMe)3]Ru) with 1.1 equiv of EtO2CNCS results in [2 + 2] cycloadditions yielding the four-membered-ring 2-iminothiete products 2a,b, respectively. Isomerization of complex 2a results in formation of 3a containing the six-membered-ring oxazinethione ligand. Alkylation of complex 3a by CH2Cl2 takes place at the thione sulfur to give 4a, which loses ethyl chloride, yielding the new six-membered-ring [1,3]-oxazin-2-one complex 5a. Further alkylation of 3a by the chloromethyl group of 5a affords the dinuclear complex 6a with two oxazin-2-one ligands bridged by a methylene group. Structures of 2b, 3a, 5a and 6a have been determined by single-crystal X-ray diffraction analysis.

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“…The isolation of 15 is consistent with the formation of [Ti(SCPh 2 )(Me 2 ATI) 2 ], as written in eq 9. Early transition metal thioaldehyde complexes have been isolated for both Ti and Zr and structurally characterized for Ti. , The same β-hydroxy thiol has been prepared by the conceptually similar reaction of equimolar amounts of thiobenzophenone, acetone and Yb metal . Reaction of [TiMe 2 (Me 2 ATI) 2 ] with thiobenzophenone and CO under our standard conditions generated 15 , as determined by 1 H NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…46,47 The same β-hydroxy thiol has been prepared by the conceptually similar reaction of equimolar amounts of thiobenzophenone, acetone and Yb metal. 48 Reaction of [TiMe 2 (Me 2 ATI) 2 ] with thiobenzophenone and CO under our standard conditions generated 15, as determined by 1 H NMR spectroscopy.…”

mentioning

confidence: 99%

Synthesis of Unsymmetrical Diolate, Oxametallacyclopentene, Amido-Alkoxide and Thiolato-Alkoxide Complexes Using Dialkyl and Diaryl Titanium Aminotroponiminate Complexes: A Route to Unsymmetrical Vicinal Diols

and

Lippard

1999

J. Am. Chem. Soc.

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The reactivity of [TiR2(Me2ATI)2] complexes, where Me2ATI = N,N ‘-dimethylaminotroponiminate, or L, with CO or RNC in the presence of various organic electrophiles has been investigated. The compounds TiMe2L2 and TiPh2L2 react with CO and aldehydes or ketones to afford unsymmetrical diolate complexes that convert to the corresponding vicinal diols after hydrolysis. Phenyl acetylene also reacts to form the oxametallacyclopentene complex [Ti(OCMe2CHCPh)(Me2ATI)2]. Treatment of TiMe2L2 with RNC yields the free imine and a source of low-valent titanium. Trapping this intermediate with 2 equiv of benzaldehyde or benzil affords the titanium diolate or enediolate complex, respectively. When 1 equiv each of benzophenone and either N-tosylbenzaldimine or acetone were added to the intermediate, [Ti(Ph2COCN(SO2tol)HPh)(Me2ATI)2] and [Ti(Ph2COCOMe2)(Me2ATI)2], respectively, were obtained. The titanium thiolato-alkoxide complex [Ti(Ph2CSCOMe2)(Me2ATI)2] was prepared by use of thiobenzophenone and acetone. This chemistry allows for the preparation of unsymmetrical diols and oxametallacyclopentene complexes from Ti(IV) dialkyls, CO, and either carbonyl compounds or alkynes. Amido-alkoxide and thiolato-alkoxide complexes can be prepared by the reaction of Ti(IV) dialkyl complex, 2 equiv of benzophenone, and either an imine or thioketone.

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Synthetic Utility of Umpoled Diaryl Thioketone−Lanthanoid Intermediates: Desulfurization, Cross Coupling with Electrophiles, and Desulfurizative Homocoupling

Cited by 26 publications

References 30 publications

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane

Synthesis of Unsymmetrical Diolate, Oxametallacyclopentene, Amido-Alkoxide and Thiolato-Alkoxide Complexes Using Dialkyl and Diaryl Titanium Aminotroponiminate Complexes: A Route to Unsymmetrical Vicinal Diols

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Synthetic Utility of Umpoled Diaryl Thioketone−Lanthanoid Intermediates: Desulfurization, Cross Coupling with Electrophiles, and Desulfurizative Homocoupling

Cited by 26 publications

References 30 publications

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites  Deprotonation and oxidation reactions

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites  Deprotonation and oxidation reactions

Reactions of Ruthenium Acetylide Complexes with EtO2CNCS: Alkylation of the Thione with Dichloromethane

Synthesis of Unsymmetrical Diolate, Oxametallacyclopentene, Amido-Alkoxide and Thiolato-Alkoxide Complexes Using Dialkyl and Diaryl Titanium Aminotroponiminate Complexes: A Route to Unsymmetrical Vicinal Diols

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Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites Deprotonation and oxidation reactions

Reactions of Ruthenium Acetylide Complexes with EtO₂CNCS: Alkylation of the Thione with Dichloromethane