- Photoinduced Copper-Catalyzed Asymmetric Decarboxylative Alkynylation with Terminal Alkynes
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We describe a photoinduced copper-catalyzed asymmetric radical decarboxylative alkynylation of bench-stable N-hydroxyphthalimide(NHP)-type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp3)?C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo- and cross-coupling catalyst but also tuning of the NHP-type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP-type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl-, allyl-, and aminocarbonyl-substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method.
- Dong, Xiao-Yang,Du, Xuan-Yi,Fang, Jia-Heng,Gu, Qiang-Shuai,Li, Zhong-Liang,Liu, Xin-Yuan,Wang, Li-Lei,Xia, Hai-Dong
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supporting information
p. 16926 - 16932
(2020/08/25)
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- Carbonylative Transformation of Allylarenes with CO Surrogates: Tunable Synthesis of 4-Arylbutanoic Acids, 2-Arylbutanoic Acids, and 4-Arylbutanals
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In this Communication, procedures for the selective synthesis of 4-arylbutanoic acids, 2-arylbutanoic acids, and 4-arylbutanals from the same allylbenzenes have been developed. With formic acid or TFBen as the CO surrogate, reactions proceed selectively and effectively under carbon monoxide gas-free conditions.
- Wu, Fu-Peng,Li, Da,Peng, Jin-Bao,Wu, Xiao-Feng
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supporting information
p. 5699 - 5703
(2019/08/01)
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- Competitive activity-based protein profiling identifies Aza-β-lactams as a versatile chemotype for serine hydrolase inhibition
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Serine hydrolases are one of the largest and most diverse enzyme classes in Nature. Most serine hydrolases lack selective inhibitors, which are valuable probes for assigning functions to these enzymes. We recently discovered a set of aza-β-lactams (ABLs) that act as potent and selective inhibitors of the mammalian serine hydrolase protein-phosphatase methylesterase-1 (PME-1). The ABLs inactivate PME-1 by covalent acylation of the enzyme's serine nucleophile, suggesting that they could offer a general scaffold for serine hydrolase inhibitor discovery. Here, we have tested this hypothesis by screening ABLs more broadly against cell and tissue proteomes by competitive activity-based protein profiling (ABPP), leading to the discovery of lead inhibitors for several serine hydrolases, including the uncharacterized enzyme α,β-hydrolase domain-containing 10 (ABHD10). ABPP-guided medicinal chemistry yielded a compound ABL303 that potently (IC50-30 nM) and selectively inactivated ABHD10 in vitro and in living cells. A comparison of optimized inhibitors for PME-1 and ABHD10 indicates that modest structural changes that alter steric bulk can tailor the ABL to selectively react with distinct, distantly related serine hydrolases. Our findings, taken together, designate the ABL as a versatile reactive group for creating first-in-class serine hydrolase inhibitors.
- Zuhl, Andrea M.,Mohr, Justin T.,Bachovchin, Daniel A.,Niessen, Sherry,Hsu, Ku-Lung,Berlin, Jacob M.,Dochnahl, Maximilian,Lopez-Alberca, Maria P.,Fu, Gregory C.,Cravatt, Benjamin F.
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supporting information; experimental part
p. 5068 - 5071
(2012/05/05)
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- N-heterocyclic carbene-mediated enantioselective addition of phenols to unsymmetrical alkylarylketenes
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Chiral N-heterocyclic carbenes (NHCs) mediate the enantioselective addition of 2-phenylphenol to unsymmetrical alkylarylketenes, delivering α-alkyl-α-arylacetic acid derivatives with good levels of enantiocontrol (up to 84% ee). Enantiodivergent stereochemical outcomes are observed using 2-phe-nylphenol and benzhydrol in the NHC-promoted esterification reaction using a triazolium precatalyst derived from pyroglutamic acid, consistent with distinct mechanistic pathways operating within these processes.
- Concellon, Carmen,Duguet, Nicolas,Smith, Andrew D.
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supporting information; experimental part
p. 3001 - 3009
(2010/03/26)
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- Asymmetric dimerization of disubstituted ketenes catalyzed by N-heterocyclic carbenes
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A series of chiral N-heterocyclic carbenes (NHCs), derived from L-pyrogutamic acid, were found to be efficient catalysts for the asymmetric dimerization of alkylarylketenes to give the corresponding α-quaternary β-alkylidenyl-β-lactones in good yields with up to 97% ee. A chiral NHC with a proximal hydroxy group is superior in comparison with the corresponding NHC with its hydroxy group protected.
- Lv, Hui,Zhang, Yan-Rong,Huang, Xue-Liang,Ye, Song
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supporting information; experimental part
p. 2715 - 2718
(2009/10/20)
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- Systematic study of chiral discrimination upon crystallisation. Part 2.1 Chiral discrimination of 2-arylalkanoic acids by (1R,2S)-2-amino-1,2-diphenylethanol
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The resolution of 2-arylalkanoic acids by (1R,2S)-2-amino-1,2-diphenylethanol has been studied. It has been found that the position of a substituent on the aromatic group of the acids affects resolution efficiency to a considerable extent. Crystal structu
- Kinbara, Kazushi,Kobayashi, Yuka,Saigo, Kazuhiko
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p. 1767 - 1775
(2007/10/03)
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- Asymmetric Decarboxylation of 2-Ethyl-2-(4-Methylphenyl)-Propane-1,3-Dioic Acid in Cholesteric Liquid Crystals
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Asymmetric decarboxylation of 2-ethyl-2-(4-methylphenyl)-propane-1,3-dioic acid was studied in some cholesteric liquid crystalline media such as 2,4-hexadienoic, benzoic, 2,4-dichlorobenzoic, and trans-cinnamic acids at 158-163 deg C, and compared with th
- Tanaka, Yoshio,Chiyo, Takayoshi,Iljima, Sei-Ichiro,Shimizu, Toshimi,Kusano, Tohru
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p. 255 - 266
(2007/10/02)
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- Process for preparing phenyl-acetic acid esters
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A process for preparing a substituted phenyl-acetic acid ester of the formula (I), SPC1 wherein R1 is an ethyl group or an isopropyl group, R2 is a hydrogen atom, a C1 -C4 alkyl group, a methoxy group, a halogen atom or a methylenedioxy group, which comprises reacting a quaternary ammonium salt of the formula (III), SPC2 wherein X is a halogen atom, and A is an alkylamine, pyridine or an N-alkylaniline, with a carboxylic acid of the formula (II), SPC3 wherein R1 and R2 are each as defined above, its reactive derivative, or a mixture of the acid and its reactive derivative.
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