170646-96-5Relevant articles and documents
Asymmetric Inverse-Electron-Demand Oxa-Diels-Alder Reaction of Allylic Ketones through Dienamine Catalysis
Shi, Ming-Lin,Zhan, Gu,Zhou, Su-Lan,Du, Wei,Chen, Ying-Chun
, p. 6480 - 6483 (2016)
A remote β,γ-regioselective asymmetric inverse-electron-demand oxa-Diels-Alder reaction between allylic ketones and α-cyano-α,β-unsaturated ketones has been developed through induced extended dienamine catalysis of a cinchona-derived primary amine. A spectrum of densely substituted dihydropyran frameworks were efficiently produced with excellent enantioselectivity and fair to exclusive diastereoselectivity.
Organocatalytic Stereoconvergent Synthesis of α-CF3 Amides: Triketopiperazines and Their Heterocyclic Metamorphosis
Foster, Robert W.,Lenz, Eva N.,Simpkins, Nigel S.,Stead, Darren
, p. 8810 - 8813 (2017)
The highly enantioselective alkylation of α-CF3 enolates, generated from triketopiperazines, has been accomplished through use of a bifunctional thiourea organocatalyst to facilitate 1,4-addition to varied enone acceptors. On treatment with appropriate nitrogen nucleophiles, the chiral triketopiperazine products undergo a metamorphosis, to provide novel fused heterocyclic lactams such as extended pyrazolopyrimidines.
Cobalt-Catalyzed Asymmetric 1,4-Reduction of β,β-Dialkyl α,β-Unsaturated Esters with PMHS
Lu, Dongpo,Lu, Peng,Lu, Zhan
supporting information, p. 4861 - 4864 (2021/09/22)
A cobalt-catalyzed asymmetric reduction of β,β-dialkyl α,β-unsaturated esters with polymethylhydrosiloxane (PMHS) was reported to deliver the corresponding esters containing a chiral trialkyl carbon center at β-position with up to 97 % yield and 98 % ee. The chiral tridentate ligand oxazoline iminopyridine (OIP) could perform well for the asymmetric reduction instead of chiral bidentate ligands. This operationally simple protocol shows a broad scope of substrates using one equivalent of readily available PMHS as a cheap and easy-to-handle reductive reagent.
Selective Construction of C?C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides
Liu, Xin,Werner, Thomas
supporting information, p. 1096 - 1104 (2020/12/31)
Herein, we report the manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon-carbon single (C?C) and carbon-carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C?C vs. C=C bonds can be controlled by the reaction conditions, namely the amount of base. The scope and limitations of the coupling reactions were thoroughly evaluated by the conversion of 21 alcohols and 15 ylides. Notably, compared to existing methods, which are based on precious metal complexes as catalysts, the present catalytic system is based on earth abundant manganese catalysts. The reaction can also be performed in a sequential one-pot reaction generating the phosphorus ylide in situ followed manganese catalyzed C?C and C=C bond formation. Mechanistic studies suggest that the C?C bond was generated via a borrowing hydrogen pathway and the C=C bond formation followed an acceptorless dehydrogenative coupling pathway. (Figure presented.).
Efficient cleavage of tertiary amide bonds: Via radical-polar crossover using a copper(ii) bromide/Selectfluor hybrid system
Maruoka, Keiji,Matsumoto, Akira,Wang, Zhe
, p. 12323 - 12328 (2020/12/08)
A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N-C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions and exhibits a broad substrate scope with respect to the tertiary amide moiety as well as to nitrogen, oxygen, and carbon nucleophiles for the subsequent derivatization. Mechanistic studies suggest that the present reaction proceeds via a radical-polar crossover process that involves benzylic carbon radicals generated by the selective radical abstraction of a benzylic hydrogen atom by the CuBr2/Selectfluor hybrid system. Furthermore, a synthetic application of this method for the selective cleavage of peptides is described. This journal is
Br?nsted Base-Catalyzed Transformation of α,β-Epoxyketones Utilizing [1,2]-Phospha-Brook Rearrangement for the Synthesis of Allylic Alcohols Having a Tetrasubstituted Alkene Moiety
Kondoh, Azusa,Tasato, Naoko,Aoki, Takuma,Terada, Masahiro
supporting information, p. 5170 - 5175 (2020/07/04)
A stereoselective transformation of α,β-epoxyketones into alkenylphosphates having a hydroxymethyl group on the β-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Br?nsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.
N-Hydroxybenzimidazole as a structurally modifiable platform forN-oxyl radicals for direct C-H functionalization reactions
Hatanaka, Miho,Jiang, Julong,Maruoka, Keiji,Matsumoto, Akira,Sakamoto, Ryu,Sakurai, Shunya,Tsuzuki, Saori,Yoshii, Tomomi
, p. 5772 - 5778 (2020/06/22)
Methods for direct functionalization of C-H bonds mediated byN-oxyl radicals constitute a powerful tool in modern organic synthesis. While severalN-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class ofN-oxyl radicals based onN-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluoridesviadirect C-H fluorination of aldehydes under mild conditions.
Simple Synthesis of Amides via Their Acid Chlorides in Aqueous TPGS-750-M
Shi, Min,Ye, Ning,Chen, Wei,Wang, Hui,Cheung, Chiming,Parmentier, Michael,Gallou, Fabrice,Wu, Bin
supporting information, p. 1543 - 1548 (2020/11/23)
The technology of surfactant chemistry is employed for amide bond construction via the reaction of acyl chlorides with amines in 2 wt % TPGS-750-M aqueous solution. Specifically, this highly efficient method enables a chromatography-free scalable process and recycling of the TPGS-750-M solution.
NOVEL CYCLIC TREX1 INHIBITORS
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Paragraph 00102, (2020/10/21)
The present invention provides compounds of Formula I: wherein, X, R1, R2, R3 and R4 are as defined herein, or a stereoisomer, tautomer, pharmaceutically acceptable salt, prodrug ester or solvate form thereof, wherein all of the variables are as defined herein. These compounds are effective at modulating the TREX1 protein and thus can be used as medicaments for treating or preventing disorders affected by the inhibition of TREX1.
Halide-Accelerated Acyl Fluoride Formation Using Sulfuryl Fluoride
Foth, Paul J.,Malig, Thomas C.,Yu, Hao,Bolduc, Trevor G.,Hein, Jason E.,Sammis, Glenn M.
supporting information, p. 6682 - 6686 (2020/09/02)
Herein, we report a new one-pot sequential method for SO2F2-mediated nucleophilic acyl substitution reactions starting from carboxylic acids. A mechanistic study revealed that SO2F2-mediated acid activation proceeds via the anhydride, which is then converted to the corresponding acyl fluoride. Tetrabutylammonium chloride or bromide accelerate the formation of acyl fluoride. Optimized halide-accelerated conditions were used to synthesize acyl fluorides in 30-80percent yields, and esters, amides, and thioesters in 72-96percent yields without reoptimization for each nucleophile.
