- Merging Halogen-Atom Transfer (XAT) and Copper Catalysis for the Modular Suzuki-Miyaura-Type Cross-Coupling of Alkyl Iodides and Organoborons
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We report here a mechanistically distinct approach to achieve Suzuki-Miyaura-type cross-couplings between alkyl iodides and aryl organoborons. This process requires a copper catalyst but, in contrast with previous approaches based on palladium and nickel
- Górski, Bartosz,Leonori, Daniele,Zhang, Zhenhua
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supporting information
(2022/02/01)
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- Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines
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The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides.
- Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
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supporting information
p. 9030 - 9033
(2017/07/11)
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- Application of Isayama–Mukaiyama cobalt catalyzed hydroperoxysilylation for the preparation of ritonavir hydroperoxide
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We report the preparation of thiazol-5-ylmethyl ((2S,3S,5S)-5-((S)-2-(3-((2-(2-hydroperoxypropan-2-yl)thiazol-4-yl)methyl)-3-methylureido)-3-methylbutanamido)-3-hydroxy-1,6-diphenylhexan-2-yl)carbamate, a hydroperoxide impurity of ritonavir also known as
- Gazal, Sharon,Gupta, Priya,Gunturu, Siva Ramakrishna,Isherwood, Matthew,Voss, Matthew E.
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p. 5099 - 5102
(2016/11/02)
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- Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O2/Et3SiH
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(Chemical Equation Presented). In the competitive peroxidation of mixtures of two alkenes with Co(II)/O2/Et3SiH, it was found that the relative reactivities of the alkene substrates are influenced by three major factors:. (1) relative stability of the intermediate carbon-centered radical formed by the reaction of the alkene with HCo(III) complex, (2) steric effects around the C=C double bond, and (3) electronic factors associated with the C=C double bond. Consistent with results from simple alkenes, the chemo-and regioselective peroxidation of dienes was also realized. Depending on the diene structure, the product included not only the expected acyclic unsaturated triethylsilyl peroxides but also 1,2-dioxolane and 1,2-dioxane derivatives via intramolecular cyclization of the unsaturated peroxy radical intermediates.
- Tokuyasu, Takahiro,Kunikawa, Shigeki,McCullough, Kevin J.,Masuyama, Araki,Nojima, Masatomo
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p. 251 - 260
(2007/10/03)
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- Co-catalyzed autoxidation of alkene in the presence of silane. The effect of the structure of silanes on the efficiency of the reaction and on the product distribution
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A systematic investigation of the structural effect of silanes on the Co-catalyzed reductive oxygenation of alkene in the presence of silane (Mukaiyama-Isayama reaction) showed that the efficiency of the reaction decreases with the increase of the steric bulk of the silanes. A similar trend was observed for the metal-exchange reaction between Co(III)-alkylperoxo complex and silane, too. The peroxidation of (S)-limonene, followed by deprotection of the derived silyl peroxides, provides a mixture of the corresponding monocyclic hydroperoxide 24 and the bicyclic one 25, the ratio being a marked function of the steric bulk of silanes.
- Wu, Jin-Ming,Kunikawa, Shigeki,Tokuyasu, Takahiro,Masuyama, Araki,Nojima, Masatomo,Kim, Hye-Sook,Wataya, Yusuke
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p. 9961 - 9968
(2007/10/03)
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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
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Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(II) (Co(thd) 2), a β-diketonate prepared in a simple one-step procedure, is an excellent catalyst for aerobic epoxidation and Mukaiyama-Isayama hydroperoxysilylation of unactivated alkenes. For hydroperoxysilylation, Co(thd)2 is superior to Co(acac)2 and can catalyse oxidation of cyclic alkenes in excellent yield. Chiral β-diketonate or keto iminato catalysts failed to catalyse this reaction in an enantioselective manner and a free radical mechanism consistent with this observation is proposed. Hydroperoxysilylation of cyclohex-1-enylmethanol by Co(thd) 2 followed by addition of a ketone/TsOH provides a simple one-pot procedure for the synthesis of spiro-1,2,4-trioxane antimalarials.
- 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.
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p. 8135 - 8138
(2007/10/03)
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- Co(III)-alkyl complex- and Co(III)-alkylperoxo complex-catalyzed triethylsilylperoxidation of alkenes with molecular oxygen and triethylsilane
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ROOCo(III) + Et3SiH → ROOSiEt3 + [HCo(III)] cat. ROOCo(III) or cat. RCo(III) R'CH=CH2 → R'CH(OOSiEt3)CH3 Et3SiH, O2 Both a Co(III)-alkyl complex and a Co(III)-alkylperoxo complex were found to catalyze triethylsilylperoxidation of alkenes with O2 and Et3SiH. On this basis, together with the nonstereoselectivity in the Co(II)-catalyzed peroxidation of 3-phenylindene and the formation of the corresponding 1,2-dioxolane from 2-phenyl-1-vinylcyclopropane (a radical clock), we propose a reasonable mechanism for the Co(II)-catalyzed novel autoxidation of alkenes with Et3SiH discovered by Isayama and Mukaiyama.
- Tokuyasu, Takahiro,Kunikawa, Shigeki,Masuyama, Araki,Nojima, Masatomo
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p. 3595 - 3598
(2007/10/03)
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- Novel Method for the Preparation of Triethylsilyl Peroxides from Olefins by the Reaction with Molecular Oxygen and Triethylsilane Catalyzed by Bis(1,3-diketonato)cobalt(II)
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In the presence of a catalytic amount of bis(1,3-diketonato)cobalt(II), various olefins react with molecular oxygen and triethylsilane at room temperature to give the corresponding triethylsilyl peroxides in high yields under neutral conditions.The reaction provides a new method for the preparation of various peroxides directly from olefins.
- Isayama, Shigeru,Mukaiyama, Teruaki
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p. 573 - 576
(2007/10/02)
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