- Water freezing as a regiocontrol element in the multicomponent assembly of cyclic enones
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Regioselective synthesis of dialkoxy 2-cyclopentenones and 2-cyclohexenones with novel substitution patterns has been accomplished by the one-pot combination of three simple starting materials (chromium carbene complex, Weinreb acetamide lithium enolate a
- De la Campa, Raquel,Flrez, Josefa
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- Enantioselective Palladium-Catalyzed Hydrophosphinylation of Allenes with Phosphine Oxides: Access to Chiral Allylic Phosphine Oxides
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A Pd-catalyzed hydrophosphinylation of alkyl and aryl-oxyallenes with phosphine oxides has been developed for the efficient and rapid construction of a family of chiral allylic phosphine oxides with a diverse range of functional groups. This methodology was further applied in the facile construction of chiral 2H-chromene and later stage functionalization of cholesterol.
- Wang, Jun,Yang, Zhiping
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p. 27288 - 27292
(2021/11/17)
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- Streamlined Catalytic Enantioselective Synthesis of α-Substituted β,γ-Unsaturated Ketones and Either of the Corresponding Tertiary Homoallylic Alcohol Diastereomers
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A widely applicable, practical, and scalable strategy for efficient and enantioselective synthesis of β,γ-unsaturated ketones that contain an α-stereogenic center is disclosed. Accordingly, aryl, heteroaryl, alkynyl, alkenyl, allyl, or alkyl ketones that contain an α-stereogenic carbon with an alkyl, an aryl, a benzyloxy, or a siloxy moiety can be generated from readily available starting materials and by the use of commercially available chiral ligands in 52-96% yield and 93:7 to >99:1 enantiomeric ratio. To develop the new method, conditions were identified so that high enantioselectivity would be attained and the resulting α-substituted NH-ketimines, wherein there is strong CN → B(pin) coordination, would not epimerize before conversion to the derived ketone by hydrolysis. It is demonstrated that the ketone products can be converted to an assortment of homoallylic tertiary alcohols in 70-96% yield and 92:8 to >98:2 dr - in either diastereomeric form - by reactions with alkyl-, aryl-, heteroaryl-, allyl-, vinyl-, alkynyl-, or propargyl-metal reagents. The utility of the approach is highlighted through transformations that furnish other desirable derivatives and a concise synthesis route affording more than a gram of a major fragment of anti-HIV agents rubriflordilactones A and B and a specific stereoisomeric analogue.
- Pozo, Juan Del,Zhang, Shaochen,Romiti, Filippo,Xu, Shibo,Conger, Ryan P.,Hoveyda, Amir H.
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p. 18200 - 18212
(2020/11/02)
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- Synthesis of Functionalized 1,3-Butadienes via Pd-Catalyzed Cross-Couplings of Substituted Allenic Esters in Water at Room Temperature
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An environmentally responsible, mild method for the synthesis of functionalized 1,3-butadienes is presented. It utilizes allenic esters of varying substitution patterns, as well as a wide range of boron-based nucleophiles under palladium catalysis, generating sp-sp2, sp2-sp2, and sp2-sp3 bonds. Functional group tolerance measured via robustness screening, along with room temperature and aqueous reaction conditions highlight the methodology's breadth and potential utility in synthesis.
- Lippincott, Daniel J.,Linstadt, Roscoe T. H.,Maser, Michael R.,Gallou, Fabrice,Lipshutz, Bruce H.
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p. 4719 - 4722
(2018/08/23)
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- Cooperative Iodide Pd(0)-Catalysed Coupling of Alkoxyallenes and N-Tosylhydrazones: A Selective Synthesis of Conjugated and Skipped Dienes
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Palladium(0)-catalysed hydro-alkylation or -alkenylation of alkoxyallenes with N-tosylhydrazones gives direct access to conjugated and skipped 1-alkoxydienes with high efficiency and excellent functional-group compatibility. The reaction is proposed to in
- Parisotto, Stefano,Palagi, Lorenzo,Prandi, Cristina,Deagostino, Annamaria
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supporting information
p. 5484 - 5488
(2018/03/27)
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- Synthesis of Functionalized [3], [4], [5] and [6]Dendralenes through Palladium-Catalyzed Cross-Couplings of Substituted Allenoates
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A mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patter
- Lippincott, Daniel J.,Linstadt, Roscoe T. H.,Maser, Michael R.,Lipshutz, Bruce H.
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p. 847 - 850
(2017/01/14)
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- AMINO COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and Γ" or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit or regulate the complement cascade. The inhibitors of Factor D described herein reduces the excessive activation of complement.
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- ETHER COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I? or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit or regulate the complement cascade. The inhibitors of Factor D described herein reduces the excessive activation of complement.
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- PHOSPHONATE COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I''' or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit
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- CARBAMATE, ESTER, AND KETONE COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I'" or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit or regulate the complement cascade. The inhibitors of Factor D described herein reduce the excessive activation of complement.
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- ALKYNE COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I'" or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit or regulate the complement cascade. The inhibitors of Factor D described herein reduce the excessive activation of complement.
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- AMIDE COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I"' or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit o
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- Pd-Catalyzed Hydroamination of Alkoxyallenes with Azole Heterocycles: Examples and Mechanistic Proposal
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Palladium-catalyzed regio- and enantioselective addition of azole heterocycles to alkoxyallenes was developed (up to 92% yields and up to 94% ee). DFT calculations suggest a new Pd(0)-driven mechanistic pathway proceeding through protonation of the Pd-coo
- Bernar, Ivan,Fiser, Béla,Blanco-Ania, Daniel,Gómez-Bengoa, Enrique,Rutjes, Floris P. J. T.
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p. 4211 - 4214
(2017/08/23)
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- ARYL, HETEROARYL, AND HETEROCYCLIC COMPOUNDS FOR TREATMENT OF IMMUNE AND INFLAMMATORY DISORDERS
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Compounds, methods of use, and processes for making inhibitors of complement Factor D are provided comprising Formula I, I" and I'" or a pharmaceutically acceptable salt or composition thereof. The inhibitors described herein target Factor D and inhibit or regulate the complement cascade. The inhibitors of Factor D described herein reduces the excessive activation of complement.
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- METHOD FOR THE PREPARATION OF alpha-SUBSTITUTED ACRYL ALDEHYDES
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The invention discloses simple and rapid method for the preparation of α-substituted acryl aldehydes. More particularly, the invention discloses a method for the preparation of α-substituted acryl aldehydes via a gold-catalysed [1,3] rearrangement of the allenyl ethers with a record turnover frequency of 4600 h?1 at 0.05 mol % of the catalyst concentration in homogeneous gold(I) catalysis. The α-substituted acryl aldehydes synthesized by the instant process are used as building blocks in organic synthesis.
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Paragraph 0098; 0099; 0100
(2016/04/19)
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- Alkoxyallene-ynes: Selective Preparation of Bicyclo[5.3.0] Ring Systems Including a δ-Alkoxy Cyclopentadienone
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The development of an intramolecular rhodium(I)-catalyzed Pauson-Khand reaction of alkoxyallene-ynes with a proximal alkoxy group is reported. This reaction, in the presence of a [Rh(cycloocta-1,5-diene)Cl]2/propane-1,3-diylbis(diphenylphosphane) system under a CO atmosphere, constitutes a powerful tool for selectively accessing carbo- A nd heterobicyclo[5.3.0] frameworks featuring an enol ether moiety. Through this procedure, a straightforward access to guaiane skeletons with a tertiary hydroxy group at the C10 position was achieved.
- Tap, Aurélien,Lecourt, Camille,Dhambri, Sabrina,Arnould, Mathieu,Galvani, Gilles,Nguyen Van Buu, Olivier,Jouanneau, Morgan,Férézou, Jean-Pierre,Ardisson, Janick,Lannou, Marie-Isabelle,Sorin, Geoffroy
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supporting information
p. 4938 - 4944
(2016/04/05)
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- Gold(i)-catalysed [1,3] O→C rearrangement of allenyl ethers
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A simple and rapid access to the α-substituted acryl aldehydes has been provided by developing a gold-catalysed [1,3] rearrangement of the allenyl ethers importantly with a record turnover frequency of 4600 h-1 (at 0.05 mol% of the catalyst concentration) in homogeneous gold(i) catalysis. The Royal Society of Chemistry.
- Kona, Chandrababu Naidu,Ramana, Chepuri V.
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supporting information
p. 2152 - 2154
(2014/02/14)
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- The palladium catalyzed asymmetric addition of oxindoles and allenes: An atom-economical versatile method for the construction of chiral indole alkaloids
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The Pd-catalyzed asymmetric allylic alkylation (AAA) is one of the most useful and versatile methods for asymmetric synthesis known in organometallic chemistry. Development of this reaction over the past 30 years has typically relied on the use of an ally
- Trost, Barry M.,Xie, Jia,Sieber, Joshua D.
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supporting information; experimental part
p. 20611 - 20622
(2012/02/01)
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- Palladium-catalyzed diastereo- and enantioselective Wagner-Meerwein shift: Control of absolute stereochemistry in the C-C bond migration event
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Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a π-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the π-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an α-chiral O-tertiary center which has various synthetic applications.
- Trost, Barry M.,Xie, Jia
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p. 6231 - 6242
(2008/12/20)
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- Palladium-catalyzed asymmetric ring expansion of allenylcyclobutanols: An asymmetric Wagner-Meerwein shift
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In this study, we developed a palladium-catalyzed atom economic asymmetric Wagner-Meerwein shift of allenylcyclobutanol substrates. It is an excellent method for creating functionalized cyclopentanones with an α-chiral O-tertiary center by ring expansion
- Trost, Barry M.,Xie, Jia
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p. 6044 - 6045
(2007/10/03)
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- Highly regioselective palladium-catalyzed annulation reactions of heteroatom-substituted allenes for synthesis of condensed heterocycles
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We have developed a highly regioselective synthesis of heterocycles via palladium-catalyzed annulation reaction of heteroatom-substituted allenes. Various aryl halides were reacted and one regioisomer was observed exclusively in all reactions. In addition
- Inamoto, Kiyofumi,Yamamoto, Akio,Ohsawa, Kazutoshi,Hiroya, Kou,Sakamoto, Takao
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p. 1502 - 1507
(2007/10/03)
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- Stereodivergent syntheses of highly substituted enantiopure 4-alkoxy-3,6-dihydro-2H-1,2-oxazines by addition of lithiated alkoxyallenes to carbohydrate-derived aldonitrones
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Additions of lithiated alkoxyallenes to D-glyceraldehyde-based nitrones 1 and 2 did not provide the expected hydroxylamine derivatives. Instead, a novel [3+3] cyclization process furnished 4-alkoxy-3,6-dihydro-2H-1,2-oxazines 9-14 with excellent syn selectivities and in moderate to good yields. Through precomplexation of the nitrones the corresponding anti-configured 1,2-oxazines 9, 10 and 13 could be obtained with high stereoselectivity. The reactions of nitrones 3-6, derived from D-erythrose or D-threose, generally proceeded less diastereoselectively, but reasonable yields of anti-configured 1,2-oxazines such as anti-17 and anti-19 could be obtained under Lewis acid promotion conditions. This was also the case for reactions of the D-arabinose-derived nitrone 7, which provided the anti-1,2-oxazines 23 and 24 with excellent diastereoselectivity and in good yields. Bisnitrone 8 and lithiated methoxyallene furnished a mixture of six compounds, among which the major component was the C2-symmetric syn/syn-1,2-oxazine 29. The diastereoselectivities of these reactions are interpreted on the basis of Dondoni's model for reactions between organolithium compounds and nitrones. The mechanisms for formation of 1,2-oxazines and of side products are discussed. The method introduced here seems to be of broad applicability and an excellent tool for diastereoselective chain elongation of carbohydrate derivatives, affording stereodefined precursors of aminopolyols and other highly functionalized compounds. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Helms, Matthias,Schade, Wolfgang,Pulz, Robert,Watanabe, Toshiko,Al-Harrasi, Ahmed,Fisera, Lubor,Hlobilova, Iva,Zahn, Gernot,Reissig, Hans-Ulrich
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p. 1003 - 1019
(2007/10/03)
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- Microwave promoted rapid isomerisation of propargyl ethers into allenyl ethers
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Aryl or alkyl propargyl ethers have been isomerized efficiently with good to excellent yield into corresponding allenyl ethers in the presence of potassium tert-butoxide under the microwave irradiation.
- Moghaddam, Firouz Matloubi,Emami, Rahdar
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p. 4073 - 4077
(2007/10/03)
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