- Insertion of carbenoids into X-H bonds catalyzed by the cyclobutadiene rhodium complexes
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The cyclobutadiene rhodium complex [(C4Et4)RhCl]2 (generated from [(C4Et4)Rh(p-xylene)]PF6 and BnNEt3Cl) catalyzes the reaction of methyl α-diazophenylacetate with RnX
- Loskutova, Natalia L.,Shvydkiy, Nikita V.,Nelyubina, Yulia V.,Perekalin, Dmitry S.
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- MALIC ENZYME INHIBITORS
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The present invention relates to novel compounds useful as malic enzyme (ME) inhibitors, processes for their preparation and use of these compounds for the therapeutic treatment of disorders mediated by ME such as cancers (e.g. pancreatic ductal adenocarcinoma (PDAC)) in humans.
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- Synthesis of Overloaded Cyclopentadienyl Rhodium(III) Complexes via Cyclotetramerization of tert-Butylacetylene
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Herein we describe the synthesis and reactivity of rhodium catalysts with the very bulky cyclopentadienyl ligand C8H3tBu4 (designated as tBu4Cp). The reaction of [Rh(cod)Cl]2 with tert-butylacetylene in the presence of Et3N gives the complex (tBu4Cp)Rh(cod) (60-65% yield), in which the cyclopentadienyl ligand tBu4Cp is assembled from four alkyne molecules. The oxidation of (tBu4Cp)Rh(cod) with chlorine or bromine gives the corresponding halide complexes (tBu4Cp)RhX2 (X = Cl (85%), Br (95%)), which have unusual 16-electron monomeric structures due to the steric shielding provided by tBu groups. A similar reaction with iodine gives the ionic dinuclear complex [(tBu4Cp)RhI3Rh(tBu4Cp)]I (99%) with halide bridges. The bromide complex (tBu4Cp)RhBr2 reacts with phosphorus ligands such as P(OMe)3, P(OPh)3, PMe2Ph, and PMePh2 to give the 18-electron adducts (tBu4Cp)RhBr2(PR3), but no reaction occurs with larger phosphines such as PPh3. The racemic chloride (tBu4Cp)RhCl2 can be separated into enantiomers by preparative TLC of its diastereomeric adducts with (R)-phenylglycinol. The complex (tBu4Cp)RhBr2 catalyzes C-H activation and annulation of O-pivaloyl-hydroxamate as well as insertion of phenyldiazoacetate into E-H bonds, although the reaction rates and the substrate scope are limited by the bulky tBu4Cp ligand.
- Kolos, Andrey V.,Nelyubina, Yulia V.,Perekalin, Dmitry S.,Sundararaju, Basker
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supporting information
p. 3712 - 3719
(2021/09/18)
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- Electrolysis promoted reductive amination of electron-deficient aldehydes/ketones: a green route to the racemic clopidogrel
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An electrocatalytic reductive amination of electron-deficient aldehydes/ketones was developed, which could be used in the synthesis of functionalized tertiary amines and large scale preparation of racemic clopidogrel. A plausible mechanism involving an iminium cation intermediate was proposed.
- Zhang, Qianyun,Zhu, Wen,Yao, Jinzhong,Zhou, Hongwei,Li, Xiaofang
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supporting information
p. 8462 - 8466
(2018/12/13)
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- A five coordination Cu(II) cluster-based MOF and its application in the synthesis of pharmaceuticals: Via sp3 C-H/N-H oxidative coupling
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Herein, a copper metal-organic framework, termed as VNU-18, containing penta-coordinated sites was successfully synthesized and fully characterized. This material was demonstrated to be an efficient heterogeneous catalyst for the oxidative C-H activation via N-H bonds. The optimized conditions are applicable for the synthesis of pharmaceuticals constructed by α-amino carbonyl skeletons.
- Tran, Thuan V.,Le, Hanh T. N.,Ha, Hiep Q.,Duong, Xuan N. T.,Nguyen, Linh H.-T.,Doan, Tan L. H.,Nguyen, Ha L.,Truong, Thanh
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p. 3453 - 3458
(2017/08/22)
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- Copper bromide reagent and its preparation method, α--aminobenzene acetone and its process for synthesis of derivatives of
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The invention discloses a copper bromide reagent, a preparation method thereof, and a synthesis method of alpha-amido propiophenone and derivative thereof. Copper bromide cheap in industry and 2,6-bi[4-(1,1-dimethyl)-2-oxazoline-2-base] pyridine react to directly obtain high yield of high-purity copper bromide reagent, in addition, the copper bromide reagent and propiophenone containing multiple important functional groups have good reaction activity. Due to the characteristic, high yield of alpha-amido propiophenone and derivative thereof can be obtained in mild conditions, conventional expensive azoic compound materials are not used, the cost is lowered to a large extent, the operation requirement is also lowered, and alpha-amido propiophenone and derivative thereof have good application prospect in industry.
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Paragraph 0035; 0036
(2017/02/28)
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- Copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals under atmosphere leading to α-aryl glycine derivatives and diarylmethylamine derivatives
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We demonstrated a copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals leading to the synthesis of α-aryl glycines and diarylmethylamines. Under an ambient atmosphere, this catalytic system could be applied to the activation of a C(sp3)-O bond of N,O-acetals with an ester and an aryl group, or without a coordinating substituent, as well as to a C(sp3)-N bond of N,N-aminals.
- Sakai, Norio,Hori, Hiroaki,Yoshida, Yoshihiro,Konakahara, Takeo,Ogiwara, Yohei
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p. 4722 - 4729
(2015/07/27)
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- Synthesis and characterization of bisoxazolines- and pybox-copper(II) complexes and their application in the coupling of α-carbonyls with functionalized amines
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Binuclear complexes [{(DMOX)CuCl}2(μ-Cl)2] (1), mononuclear complexes [(DMOX)CuBr2] (2) (DMOX = 4,5-dihydro-2-(4,5- dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyloxazole) and the pybox Cu(ii) complex [(Dm-Pybox)CuBr2/
- Jia, Wei-Guo,Li, Dan-Dan,Dai, Yuan-Chen,Zhang, Hui,Yan, Li-Qin,Sheng, En-Hong,Wei, Yun,Mu, Xiao-Long,Huang, Kuo-Wei
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supporting information
p. 5509 - 5516
(2014/07/21)
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- Simple catalytic mechanism for the direct coupling of α-carbonyls with functionalized amines: A one-step synthesis of plavix
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The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino-substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst is reconstituted. The practical value of this transformation is highlighted through one-step syntheses of two high-profile pharmaceutical agents, Plavix and amfepramone.
- Evans, Ryan W.,Zbieg, Jason R.,Zhu, Shaolin,Li, Wei,Macmillan, David W. C.
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supporting information
p. 16074 - 16077
(2013/11/19)
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- Copper-catalyzed amination of silyl ketene acetals with N-chloroamines
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A copper(I)/2,2′-bipyridyl complex catalyzes an amination reaction of silyl ketene acetals with N-chloroamines, presenting a new preparative method of α-amino esters.
- Miura, Tomoya,Morimoto, Masao,Murakami, Masahiro
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supporting information
p. 5214 - 5217,4
(2020/09/02)
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- Microwave assisted Petasis boronic-Mannich reactions
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We have used a design of experiments (DOE) approach to optimise rapidly a set of microwave assisted conditions for the Petasis reaction. The optimal conditions involved the microwave heating of the reaction components in dichloromethane (1M concentration)
- McLean, Neville J.,Tye, Heather,Whittaker, Mark
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p. 993 - 995
(2007/10/03)
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