- A Bulky Disulfoxide Ligand for Pd-Catalyzed Oxidative Allylic C-H Amination with 2,2,2-Trichloroethyl Tosyl Carbamate
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Challenging substrates and conditions in homogeneous catalysis pose stringent demands on the ligands used. A novel, bulky, 1-adamantyl-substituted disulfoxide ligand designed after a systematic evaluation of the electronic and steric properties of disulfoxide substituents permits the allylic oxidative C-N coupling reaction to proceed at lower catalyst loading while requiring a smaller excess of reagents. Additionally, this ligand improves the yields when TsNHCOOCH2CCl3, a novel reagent that permits deprotection of the products under both acidic and basic conditions, is used.
- Li, You-Gui,Li, Li,Yang, Ming-Yue,He, Gang,Kantchev, Eric Assen B.
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p. 4907 - 4917
(2017/05/12)
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- Regio- and stereoselective allylic C-H arylation with electron-deficient arenes by 1,1′-Bi-2-naphthol-palladium cooperation
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A palladium-catalyzed allylic C-H arylation reaction with electron-deficient arenes with high regio- and stereoselectivity is reported. This work represents the first successful use of 1,1′-bi-2-naphthol as the ancillary ligand in allylic C-H activation, which is the key factor for chemoselectivity. Furthermore, high selectivity allylic C-H acetoxylation and amination were also successfully achieved under the same catalytic system.
- Wang, Gang-Wei,Zhou, An-Xi,Li, Shi-Xia,Yang, Shang-Dong
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supporting information
p. 3118 - 3121
(2014/06/23)
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- Palladium-catalyzed allylic C-H amination of alkenes with N-fluorodibenzenesulfonimide: Water plays an important role
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A new palladium-catalyzed highly regioselective allylic C-H amination of alkenes with NFSI in the presence of a catalytic amount of water was developed and successfully expanded to Selectfluor-mediated palladium-catalyzed aminations of alkenes with N-tosy
- Xiong, Tao,Li, Yan,Mao, Lujia,Zhang, Qian
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supporting information; experimental part
p. 2246 - 2248
(2012/03/27)
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- Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: Insights into the effect of naphthoquinone
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Palladium-catalyzed oxidative amination of unactivated alkyl olefins has been developed to produce linear (E)-allylimides with high regioselectivity. This highly efficient transformation of alkenes has been achieved by enhancing the reoxidation of palladi
- Yin, Guoyin,Wu, Yichen,Liu, Guosheng
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supporting information; experimental part
p. 11978 - 11987
(2010/11/02)
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- Palladium-catalyzed intermolecular aerobic oxidative amination of terminal alkenes: Efficient synthesis of linear allylamine derivatives
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(Chemical Equation Presented) O2-coupledallylic C-H amination: A first general palladium-mediated intermolecular aerobic oxidative allylic amination was developed to synthesize linear (E)-allylimides with high regioselectivity (see scheme; MA = maleic anhydride). The proposed mechanism involves an allylic C-H activation with subsequent nitrogen nucleophile substitution. The catalytic system allows efficient dioxygen-coupled turnover without additional cocatalysts.
- Liu, Guosheng,Yin, Guoyin,Wu, Liang
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supporting information; body text
p. 4733 - 4736
(2009/02/06)
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- Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis
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A novel heterobimetallic Pd(II)sulfoxide/(salen)Cr(III)Cl-catalyzed intermolecular linear allylic C-H amination (LAA) is reported. This reaction directly converts densely functionalized α-olefin substrates (1 equiv) to linear (E)-allylic carbamates with good yields and outstanding regio- and stereoselectivities (>20:1). Chiral bis-homoallylic and homoallylic oxygen, nitrogen, and carbon substituted α-olefins undergo allylic C-H amination with good yields, excellent selectivities, and no erosion in enantiomeric purity. Streamlined routes to (E)-allylic carbamates that can be further elaborated to medicinally and biologically relevant allylic amines are also demonstrated. Valuable 15N-labeled allylic amines may be generated directly from allyl moieties at late stages of synthetic routes by using the readily available 15N-(methoxycarbonyl)-p-toluenesulfonamide nucleophile. Evidence is provided that this reaction proceeds via a heterobimetallic mechanism where Pd/sulfoxide mediates allylic C-H cleavage to form a π-allylPd intermediate, and (salen)Cr(III)Cl/BQ work together to promote functionalization with the nitrogen nucleophile. Copyright
- Reed, Sean A.,White, M. Christina
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p. 3316 - 3318
(2008/10/09)
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