- Asymmetric Synthesis and Application of Chiral Spirosilabiindanes
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Reported here is the development of a class of chiral spirosilabiindane scaffolds by Rh-catalyzed asymmetric double hydrosilation, for the first time. Enantiopure SPSiOL (spirosilabiindane diol), a new type of chiral building block for the preparation of various chiral ligands and catalysts, was readily prepared on greater than 10 gram scale using this protocol. The potential of this new spirosilabiindane scaffold in asymmetric catalysis was preliminarily demonstrated by development of the corresponding monodentate phosphoramidite ligands (SPSiPhos), which were used in both a Rh-catalyzed hydrogenation and a Pd-catalyzed intramolecular carboamination.
- Chang, Xin,Chen, Hong-Chao,Li, Chuan-Ying,Ma, Pei-Long,Wang, Peng
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- One-Pot Asymmetric Synthesis of Alkylidene 1-Alkylindan-1-ols Using Br?nsted Acid and Palladium Catalysis
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A one-pot catalytic enantioselective allylboration/Mizoroki-Heck reaction of 2-bromoaryl ketones has been developed for the asymmetric synthesis of 3-methyleneindanes bearing a tertiary alcohol center. Br?nsted acid-catalyzed allylboration with a chiral BINOL derivative was followed by a palladium-catalyzed Mizoroki-Heck cyclization, resulting in selective formation of the exo-alkene. This novel protocol provides a concise and scalable approach to 1-alkyl-3-methyleneindan-1-ols in high enantiomeric ratios (up to 96:4 er). The potential of these compounds as chiral building blocks was demonstrated with efficient transformation to optically active diol and amino alcohol scaffolds.
- Faggyas, Réka J.,Calder, Ewen D. D.,Wilson, Claire,Sutherland, Andrew
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- Intramolecular One-Carbon Homologation of Unstrained Ketones via C-C Activation-Enabled 1,1-Insertion of Alkenes
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Here, we describe the development of a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp2)-C(sp3) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.
- Huang, Jiangkun,Zhang, Rui,Wu, Xiuli,Dong, Guangbin,Xia, Ying
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supporting information
p. 2436 - 2440
(2022/04/07)
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- The intramolecular reaction of acetophenoneN-tosylhydrazone and vinyl: Br?nsted acid-promoted cationic cyclization toward polysubstituted indenes
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In the presence of TsNHNH2, a Br?nsted acid-promoted intramolecular cyclization ofo-(1-arylvinyl) acetophenone derivatives was developed, leading to polysubstituted indenes with complexity and diversity in moderate to excellent yields. In sharp contrast with either the radical or carbene involved cyclization of aldehydicN-tosylhydrazone with vinyl, a cationic cyclization pathway was involved, whereN-tosylhydrazone served as an electrophile and alkylation reagent during this transformation.
- Wang, Zhixin,Li, Yang,Chen, Fan,Qian, Peng-Cheng,Cheng, Jiang
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p. 1810 - 1813
(2021/02/27)
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- Divergent Access to Benzocycles through Copper-Catalyzed Borylative Cyclizations
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A copper-catalyzed chemodivergent approach to five- and six-membered benzocycles from dienyl arenes tethered with a ketone has been developed. Through proper choice of coordinating ligands and catalytic conditions, copper-catalyzed borylative cyclization of a single dienyl arene can be diverted to two different pathways, leading to indanols and dihydronaphthalenols with high stereoselectivity. The chiral bidentate bisphosphine ligand (S,S)-Ph-BPE was optimal for asymmetric copper-allyl addition to a tethered ketone via a boat-like transition state, whereas NHC ligands led to boro-allyl addition producing indanols with high diastereoselectivity. (Figure presented.).
- Yoon, Wan Seok,Han, Jung Tae,Yun, Jaesook
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p. 4953 - 4959
(2021/09/14)
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- Synthesis Development of the Selective Estrogen Receptor Degrader (SERD) LSZ102 from a Suzuki Coupling to a C-H Activation Strategy
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The development of the synthetic process to the selective estrogen receptor degrader (SERD) drug candidate LSZ102 from the medicinal chemistry synthesis to the streamlined large-scale manufacturing route is described. The synthesis of LSZ102 could be sign
- Baenziger, Markus,Baierl, Marcel,Devanathan, Krishnaswamy,Eswaran, Sumesh,Fu, Peng,Gschwend, Bjoern,Haller, Michael,Kasinathan, Gopu,Kovacic, Nikola,Langlois, Audrey,Li, Yongfeng,Schuerch, Friedrich,Shen, Xiaodong,Wan, Yinbo,Wickendick, Regina,Xie, Siwei,Zhang, Kai
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supporting information
p. 1405 - 1419
(2020/10/12)
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- Asymmetric Synthesis of 1,2-Dihydronaphthalene-1-ols via Copper-Catalyzed Intramolecular Reductive Cyclization
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We describe a copper-catalyzed intramolecular reductive cyclization of easily accessible benz-tethered 1,3-dienes containing a ketone moiety. This process provided biologically active 1,2-dihydronaphthalene-1-ol derivatives in good yields with excellent enantio- and diastereoselectivity. Mechanistic investigations using density functional theory revealed that (Z)- and (E)-allylcopper intermediates formed in situ from the diene and copper catalyst undergo isomerization and selective intramolecular allylation of the (E)-allylcopper form of the major product through a six-membered boatlike transition state. The resulting products were further transformed to fully saturated naphthalene-1-ols by reactions of the olefin moiety.
- Acharyya, Ranjan Kumar,Kim, Soyoung,Park, Yeji,Han, Jung Tae,Yun, Jaesook
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p. 7897 - 7902
(2020/11/02)
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- 6,7-DIHYDRO-4H-PYRAZOLO[1,5-A]PYRAZINE INDOLE-2-CARBOXAMIDES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to antiviral agents. Specifically, the present invention relates to compounds of formula I which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for making the compounds.
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Page/Page column 74
(2020/05/29)
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- NOVEL 6,7-DIHYDRO-4H-PYRAZOLO[1,5-A]PYRAZINE INDOLE-2-CARBOXAMIDES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to novel antiviral agents. Specifically, the present invention relates to compounds which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for mating the compounds.
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Page/Page column 76
(2020/05/29)
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- NOVEL OXALYL PIPERAZINES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to novel antiviral agents. Specifically, the present invention relates to compounds which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for making the compounds.
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Page/Page column 92
(2020/11/12)
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- NOVEL INDOLE-2-CARBOXAMIDES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to novel antiviral agents. Specifically, the present invention relates to compounds which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for making the compounds.
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Page/Page column 111
(2020/11/13)
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- NOVEL, HIGHLY ACTIVE PYRAZOLO-PIPERIDINE SUBSTITUTED INDOLE-2-CARBOXAMIDES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to novel antiviral agents. Specifically, the present invention relates to compounds which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for making the compounds.
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Page/Page column 99
(2019/05/22)
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- NOVEL, HIGHLY ACTIVE AMINO-THIAZOLE SUBSTITUTED INDOLE-2-CARBOXAMIDES ACTIVE AGAINST THE HEPATITIS B VIRUS (HBV)
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The present invention relates generally to novel antiviral agents. Specifically, the present invention relates to compounds which can inhibit the protein(s) encoded by hepatitis B virus (HBV) or interfere with the function of the HBV replication cycle, compositions comprising such compounds, methods for inhibiting HBV viral replication, methods for treating or preventing HBV infection, and processes and intermediates for making the compounds.
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Page/Page column 127
(2019/05/22)
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- PdII-Catalyzed Oxidative Tandem aza-Wacker/Heck Cyclization for the Construction of Fused 5,6-Bicyclic N,O-Heterocycles
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A PdII-catalyzed oxidative tandem cyclization was developed for the construction of fused 5,6-bicyclic N, O-heterocycles. This reaction was enabled by the combined use of a 3-methylpyridine ligand and pentafluorobenzoic acid additive. A range of heterocyclic products with different substituents could be prepared in moderate to good yields via this methodology. Several transformations, including a scaled-up preparation of product 2 a, were also carried out showing the good applicability of our methodology.
- Ye, Chenghao,Kou, Xuezhen,Xia, Jingzhao,Yang, Guoqiang,Kong, Li,Wei, Quhao,Zhang, Wanbin
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p. 1897 - 1901
(2018/07/31)
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- Preparation of isoindolinones via a palladium-catalyzed diamination
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A Pd(II)-catalyzed cyclization using oxidative olefin diamination was developed for the preparation of isoindolinones from ortho-olefinic N-methoxybenzamides. Using the optimized reaction conditions, the desired products were obtained in up to 90% yield using NFSI as the oxidant. This reaction provides an efficient and direct access to isoindolinones with amine functionality, an important drug skeleton.
- Li, Yu,Kou, Xuezhen,Ye, Chenghao,Zhang, Xinghua,Yang, Guoqiang,Zhang, Wanbin
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p. 285 - 288
(2017/01/03)
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- Facile synthesis of 1-naphthols through a copper-catalyzed arylation of methyl ketones with o-bromoacetophenones
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The coupling reactions of simple methyl ketones with o-bromoacetophenones and subsquential cyclization reactions were realized to produce a range of 1-naphthols. These cascade reactions were initiated by a rare Cu-catalyzed arylation reaction of methyl ketones with aromatic bromides.
- Lou, Zhen-Bang,Pang, Xin-Long,Chen, Chao,Wen, Li-Rong,Li, Ming
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p. 1231 - 1235
(2015/12/30)
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- Palladium-Catalyzed Aerobic Aminooxygenation of Alkenes for Preparation of Isoindolinones
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A palladium-catalyzed intramolecular isoindolinone-forming aminooxygenation of alkenes with 1 atm of oxygen as oxidant is reported. A variety of functionalized alkenes and carboxylic acids can be used, and high yields were observed. Preliminary mechanistic studies revealed that the aminooxygenation products were formed through the oxidation of a C-PdII species using a strong oxidant, peroxide, which is generated in situ from a Pd(OAc)2/bpy/O2/HOAc catalytic system.
- Kou, Xuezhen,Li, Yu,Wu, Liang,Zhang, Xinghua,Yang, Guoqiang,Zhang, Wanbin
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supporting information
p. 5566 - 5569
(2015/12/01)
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- Cobalt-catalyzed enantioselective intramolecular hydroacylation of ketones and olefins
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Cobalt-chiral diphoshine catalytic systems promote intramolecular hydroacylation reactions of 2-acylbenzaldehydes and 2-alkenylbenzaldehydes to afford phthalide and indanone derivatives, respectively, in moderate to good yields with high enantioselectivities. The ketone hydroacylation did not exhibit a significant H/D kinetic isotope effect (KIE) with respect to the aldehyde C-H bond, indicating that C-H activation would not be involved in the rate-limiting step.
- Yang, Junfeng,Yoshikai, Naohiko
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p. 16748 - 16751
(2015/02/05)
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- Base-catalyzed synthesis of substituted indazoles under mild, transition-metal-free conditions
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Back to basics: A transition-metal-free method developed for the synthesis of indazoles involves an inexpensive catalytic system composed of a diamine and K2CO3. Various (Z)-2-bromoacetophenone tosylhydrazones were converted into indazoles at room temperature in excellent yields (see example; Ts=p-toluenesulfonyl). The yield was improved by photoisomerization with UV light when E/Z isomeric mixtures of the starting material were used. Copyright
- Thome, Isabelle,Besson, Claire,Kleine, Tillmann,Bolm, Carsten
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supporting information
p. 7509 - 7513
(2013/07/26)
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- Intramolecular σ-bond metathesis between carbon-carbon and silicon-silicon bonds
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An intramolecular σ-bond metathesis between carbon-carbon and silicon-silicon bonds took place on treatment of a disilane tethered to a cyclobutanone with a palladium(0) catalyst, furnishing a silaindane skeleton as well as an acylsilane functionality at
- Ishida, Naoki,Ikemoto, Wataru,Murakami, Masahiro
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supporting information; experimental part
p. 3230 - 3232
(2012/09/08)
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- Silver-catalysed intramolecular cyclisation of 2-alkynylacetophenones and 3-acetyl-2-alkynylpyridines in the presence of ammonia
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Silver-catalysed/microwave-assisted domino reactions of 2-alkynyl-acetophenones and 3-acetyl-2-alkynylpyridines in the presence of ammonia are widely described. In most cases the reaction give a mixture of the imino- and carbo-cyclisation products, with a
- Dell'Acqua, Monica,Abbiati, Giorgio,Arcadi, Antonio,Rossi, Elisabetta
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p. 7836 - 7848
(2011/12/02)
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- MACROCYCLIC INDOLE DERIVATIVES USEFUL AS HEPATITIS C VIRUS INHIBITORS
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Inhibitors of HCV replication of formula (I) including stereochemically isomeric forms, and salts, hydrates, solvates thereof, wherein R1, R2, R4, R5, R6 and R7 have the meaning defined in the claims. The present invention also relates to processes for preparing said compounds, pharmaceutical compositions containing them and their use in HCV therapy.
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Page/Page column 87-88
(2010/04/03)
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- PROCESS FOR THE PRODUCTION OF FUSED, TRICYCLIC SULFONAMIDES
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The present invention provides methods, i.e., scalable or large-scale processes for the production of fused, tricyclic sulfonamido analogs, such as substituted or unsubstituted 5- (aryl-sulfonyl)-4,5-dihydro- 1H-pyrazolo[4,3-c]quinolines and 5-(heteroaryl-sulfonyl)-4,5- dihydro-1H-pyrazolo[4,3-c]quinolines. Exemplary methods of the invention include an intra-molecular cyclization step, in which a carbon-nitrogen bond is formed, and which employs a copper-based catalyst that contains at least one organic ligand, such as DMEDA. The invention further provides compounds, which are useful as intermediates in the methods of the invention.
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Page/Page column 99
(2010/11/04)
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- Processes for preparing 6-alkyl-5-arylsulfonyl-dihydrophenanthridines
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Synthetic methods are provided for production of compounds of the formula: where R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are as defined in the specification.
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Page/Page column 10
(2010/02/15)
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