Co(thd)2: a superior catalyst for aerobic epoxidation and hydroperoxysilylation of unactivated alkenes: application to the synthesis of spiro-1,2,4-trioxanes

O’Neill, Paul M.; Hindley, Stephen; Pugh, Matthew D.; Davies, Jill; Bray, Patrick G.; Park, B.Kevin; Kapu, Dauda S.; Ward, Stephen A.; Stocks, Paul A.

doi:10.1016/j.tetlet.2003.09.033

Cited by 73 publications

(51 citation statements)

References 13 publications

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“…117 These authors have shown that use of Co(dpm) 2 instead of Co(acac) 2 in the Mukaiyama/Isayama silylhydroperoxidation 103,104 results in modest to significantly improved yields.…”

Section: C-o Bondsmentioning

confidence: 99%

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

et al. 2016

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Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions.

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“…117 These authors have shown that use of Co(dpm) 2 instead of Co(acac) 2 in the Mukaiyama/Isayama silylhydroperoxidation 103,104 results in modest to significantly improved yields.…”

Section: C-o Bondsmentioning

confidence: 99%

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

et al. 2016

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“…Anhydrous 1-methyl-2-pyrrolidinone (NMP) and cobalt(II) acetylacetonate were purchased from Acros and used as received. (E)-1-Iodo-1-octene [12], butylzinc iodide [13], and compounds 1, 2, 3, and 5 were synthesized via literature procedures [14][15][16]. GC analysis was performed on a Shimadzu GC-2010 Series gas chromatograph with a Shimadzu SH-5 column.…”

Section: Methodsmentioning

confidence: 99%

Modified cobalt(II) acetylacetonate complexes as catalysts for Negishi-type coupling reactions: influence of ligand electronic properties on catalyst activity

Struzinski

Gohren

MacArthur

2009

Transition Met Chem

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Four known electronically diverse cobalt(II) acetylacetonate derivatives were synthesized by replacement of the acetylacetonate methyl groups with combinations of tert-butyl, ethoxy, and trifluoromethyl groups in order to study the effect of catalyst electronic properties on the reaction rate and product yield of the cobalt-catalyzed reaction between haloalkenes and butylzinc iodide. Infrared spectroscopy of these compounds showed an increase in the CO stretching frequency as the ligand substituents became more electron withdrawing. These compounds, in addition to cobalt(II) acetylacetonate itself, were evaluated as catalysts for the coupling reaction between (E)-1-iodo-1-octene and butylzinc iodide to form (E)-5-dodecene. Faster reaction rates were observed and higher yields of 5-dodecene were produced when catalysts containing electron-donating ligands were employed. Side reactions, including the homocoupling of 1-iodo-1-octene to produce 7,9-hexadecadiene, were also observed under the reported reaction conditions. The rate of side-product formation was more competitive with the rate of the cross-coupling reaction when slower, electron-deficient catalysts were employed.

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“…O'Neill and co-workers reasoned that a structurally similar catalyst derived from 2,2,6,6-tetramethylheptane-3,5-dione, namely (Co(thd) 2 ), would have comparable electronic properties to Co(modp) 2 and would be easier to prepare. 11 The b-diketonate was prepared in a simple, one-step process and successfully induced the hydroperoxysilylation of unactivated alkenes, outperforming Co(acac) 2 for all substrates tested.…”

Section: Isayama-mukaiyama Reactionmentioning

confidence: 99%

“…41 Following extensive screening studies and reaction optimization, it was discovered that Cu(ClO 4 ) 2 $6H 2 O was the most efficient catalyst, outperforming Cu(acac) 2 , Fe(acac) 2 and Mn(OAc) 2 $4H 2 O. A selective, gram-scale method was developed for the synthesis of a-peroxidated derivatives of b-diketones, bketoesters and diethyl malonate, with the target compounds recovered in high yields from b-diketones (Table 10, entries 1-5), lower yields from b-keto esters (entries 6-10) and lowest yields from malonates (entries [11][12][13][14]. The mechanism proceeds by initial complexation of the dicarbonyl with Cu(II), followed by reaction with the tert-butylperoxy radical to form the target peroxide and monovalent copper.…”

Section: Kharasch and Related Reactionsmentioning

confidence: 99%

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Advances in the synthesis of acyclic peroxides

et al. 2017

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Peroxide-containing compounds are an attractive synthetic target, given their widespread abundance in nature, with many displaying potent antimalarial and antimicrobial properties. This review summarises the many developments in the synthesis of acyclic peroxides, with a particular focus on the past 20 years, and seeks to update organic chemists about these new approaches. The synthetic methodologies have been subdivided into metal-catalysed reactions, organocatalytic reactions, direct oxidation reactions, miscellaneous reactions and enzymatic routes to acyclic peroxides

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Co(thd)2: a superior catalyst for aerobic epoxidation and hydroperoxysilylation of unactivated alkenes: application to the synthesis of spiro-1,2,4-trioxanes

Cited by 73 publications

References 13 publications

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

Modified cobalt(II) acetylacetonate complexes as catalysts for Negishi-type coupling reactions: influence of ligand electronic properties on catalyst activity

Advances in the synthesis of acyclic peroxides

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