- LONG-ACTING CONTRACEPTIVE AGENTS: ESTER OF NORETHISTERONE WITH α- AND/OR β-CHAIN BRANCHING
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The synthesis of eighteen esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) is described.These all possess some form of α- and/or β-substitution in the ester side-chain.The work was undertaken in order to evaluate any long-acting fertility control effect intrinsic in such compounds.A pentamethyl disiloxy ether was also included in the group of substances prepared for testing because of its similar substitution pattern.
- Watson, T. G.,Hosking, M.,Herz, J. E.,Torres, J. V.,Muller, J.,et al.
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- Dynamically stable helices of poly(N-propargylamides) with bulky aliphatic groups
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N-Propargylamides with bulky pendent groups [HC≡CCH2NHCOR, 9: R = CH2C(CH3)3, 10: R=C(CH 3)3 11: R = C(CH3)2CH 2CH2CH3,12: R = CH(CH2CH 3)2, 13: R = CH(CH2CH2CH 3)2] were polymerized with a rhodium catalyst, (nbd)Rh+B-(C8H5)4 (nbd = 2,5-norbornadiene), to obtain the polymers in 80-92% yields. Poly(11) and poly(12) possessed moderate molecular weights (Mn ≥ 10 000) and were totally soluble in a few solvents including chloroform. On the other hand, the Mn values of poly(9), poly(10), and poly(13) were no more than 5000, and these polymers were not completely soluble in any solvents. The conformational transition behavior of these polymers was examined by temperature-variable UV-vis spectroscopy in chloroform solution, which revealed that poly(10) - poly(13) could form dynamically stable helical conformation even at 60°C. By copolymerizations of monomers 9 and 10 with monomer 4, HC≡CCH2NHCO(CH2)4H, the solubility of the polymers was effectively improved and almost all the copolymers totally dissolved in chloroform, while the molecular weights of the copolymers increased up to 18 600-45 000. Moreover, the helix contents of poly(40.63-co- 90.37) and poly(40.40-co-100.60) were the highest among the two series of (co)polymers, respectively. It is concluded that the copolymerization of 9 and 10 with 4 effectively decreased the steric repulsion between the crowded side chains, which probably allowed the copolymers to take helical conformation efficiently.
- Deng, Jianping,Tabei, Junichi,Shiotsuki, Masashi,Sanda, Fumio,Masuda, Toshio
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- Pd/Cu-Catalyzed Cascade C(sp3)-H Arylation and Intramolecular C-N Coupling: A One-Pot Synthesis of 3,4-2 H-Quinolinone Skeletons
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In this letter, we successfully explored a cascade Pd/Cu-catalyzed intermolecular C(sp3)-H arylation of amides and intramolecular C-N coupling reaction. This method provides a one-pot strategy to synthesize 3,4-2H-quinolinone with good regioselectivity of C-H arylation and C-N coupling from C-I and C-X bonds from readily available starting materials.
- Xiao, Han-Zhi,Wang, Wen-Shu,Sun, Yu-Song,Luo, Hao,Li, Bo-Wen,Wang, Xiao-Dong,Lin, Wei-Li,Luo, Fei-Xian
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supporting information
p. 1668 - 1671
(2019/03/11)
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- COMPOSITIONS AND METHODS OF MAKING EXPANDED HEMATOPOIETIC STEM CELLS USING PTEN INHIBITORS
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This invention is directed to, inter alia, compounds, methods, systems, and compositions for the maintenance, enhancement, and expansion of hematopoietic stem cells derived from sources of non-mobilized peripheral blood. Also provided herein are compounds of Formula I which are useful in maintaining, enhancing, and expanding of hematopoietic stem cells.
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Paragraph 0325
(2018/12/13)
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- Copper(II)-mediated intermolecular amination of inert C(sp3)[sbnd]H bonds with simple alkylamines to construct α,α-disubstituted β-amino acid derivatives
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Disclosed herein is a copper(II)-mediated chelation-assisted intermolecular amination of inert C(sp3)[sbnd]H bonds using simple alkylamines as the amino source. A straightforward and step-economic alternative to α,α-disubstituted β-amino acid derivatives is provided consequently. This reaction features good functional group tolerance and relatively broad substrate scope. Furthermore, a coupling product between morpholine and radical inhibitor 2,6-di-tert-butyl-p-cresol (BHT) was isolated, indicating that a single electron transfer (SET) process might be involved in this transformation.
- Wang, Chunxia,Yang, Yudong
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supporting information
p. 935 - 940
(2017/02/18)
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- Nickel-Catalyzed Aminoxylation of Inert Aliphatic C(sp3)-H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α-Formyl Acid Derivatives
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Nickel-catalyzed aminoxylation of an unactivated C(sp3)-H bond with a stable nitroxyl radical has been accomplished for the first time to offer various N-alkoxyamine derivatives, which further enables a one-pot approach to α-formyl acid derivatives. The aminoxylation process reported also provides direct evidence for the oxidative addition of a cyclometallic intermediate with a free radical, which is helpful for the reaction-mechanism study in transition-metal-catalyzed functionalization of inert C(sp3)-H bonds.
- Wang, Chunxia,Zhang, Luoqiang,You, Jingsong
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supporting information
p. 1690 - 1693
(2017/04/11)
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- Nickel-Catalyzed oxidative coupling of unactivated C(sp3)-H bonds in aliphatic amides with terminal alkynes
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In this work, we demonstrated Ni-catalyzed oxidative coupling of unactivated C(sp3)-H bonds with terminal alkynes for construction of C(sp3)-C(sp) bonds to synthesize alkyl-substituted internal alkynes. Different amides exhibited good compatibility. Preliminary mechanistic studies were conducted to account for this alkynylation.
- Luo, Fei-Xian,Cao, Zhi-Chao,Zhao, Hong-Wei,Wang, Ding,Zhang, Yun-Fei,Xu, Xing,Shi, Zhang-Jie
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supporting information
p. 18 - 21
(2017/04/04)
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- Copper(II)/Silver(I)-Catalyzed Sequential Alkynylation and Annulation of Aliphatic Amides with Alkynyl Carboxylic Acids: Efficient Synthesis of Pyrrolidones
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A highly efficient protocol for the synthesis of pyrrolidones by the copper-catalyzed alkynylation/annulation of aliphatic amides with alkynyl carboxylic acids is discussed in this paper. A broad range of easily accessible alkynyl carboxylic acids were introduced at the β-methyl group of aliphatic amides with the assistance of an 8-aminoquinolyl auxiliary group via decarboxylation to achieve the subsequent cyclic C-N bond formation within one hour. High selectivity of β-methyl groups over methylene groups was observed, and the extension of this catalytic system to the activation of methylene C-H bonds failed. The substrates with two different groups at the α-position of the aliphatic amides lead to the formation of diastereoisomers which is determined by 1H NMR spectroscopy. The initially produced products with Z-configurations can be easily transformed to the corresponding products with E-configurations by the treatment with dilute p-toluenesulfonic acid after the reaction. This catalytic tandem decarboxylative cyclization provides a new opportunity for the direct functionalization of sp3 C-H bonds.
- Zhang, Jitan,Li, Danyang,Chen, Hui,Wang, Binjie,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 792 - 807
(2016/03/09)
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- Nickel-catalyzed direct thioetherification of β-C(sp3)-H bonds of aliphatic amides
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The nickel-catalyzed β-thioetherification of unactivated C(sp3)-H bond of propionamides is established with the assistance of 8-aminoquinoline auxiliary, leading to the β-thio carboxylic acid derivatives. A broad range of functional groups is compatible with this thioetherfication reaction. The process represents the first successful example of metal-catalyzed C-S bond formation from unactivated C(sp3)-H bonds.
- Lin, Cong,Yu, Wenlong,Yao, Jinzhong,Wang, Bingjie,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 1340 - 1343
(2015/03/14)
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- Copper-mediated aryloxylation and vinyloxylation of β-C(sp3)-H bond of propionamides with organosilanes
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A novel copper-mediated method for the aryloxylation and vinyloxylation of β-C(sp3)-H bonds of propioamides with organosilanes is described. The reaction proceeds with the assistance of an 8-aminoquinolyl auxiliary in a tandem way by the first oxidation of β-C(sp3)-H bonds and subsequent arylation/vinylation to give the aryloxylation/vinyloxylation products. This unusual aryloxy/vinyloxy forming reaction offers a new avenue for the functionalization of unactivated sp3 C-H bonds in organic synthesis.
- Zhang, Jitan,Chen, Hui,Wang, Binjie,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 2768 - 2771
(2015/06/16)
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- Cobalt-Catalyzed Cyclization of Aliphatic Amides and Terminal Alkynes with Silver-Cocatalyst
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A new method of cobalt-catalyzed synthesis of pyrrolidinones from aliphatic amides and terminal alkynes was discovered through a C-H bond functionalization process on unactivated sp3 carbons with the silver cocatalyst using a bidentate auxiliary. For the first time, a broad range of easily accessible alkynes are exploited as the reaction partner in C(sp3)-H bond activation to give the important 5-ethylidene-pyrrolidin-2-ones in a site-selective fashion. The reaction tolerates a wide variety of functional groups including -F, -Cl, -Br, -CF3, ether, cyclopropane, and thiophene. Both pyridine ligand and aromatic solvent play the important role for the promotion of reactivity. This cobalt-catalyzed cyclization reaction can be successfully extended to a variety of aromatic amides to afford a variety of isoindolinones. Attractive features of this catalytic system include its low cost, easy operation, and convenient access to a wide range of pyrrolidinones and isoindolinones.
- Zhang, Jitan,Chen, Hui,Lin, Cong,Liu, Zhanxiang,Wang, Chen,Zhang, Yuhong
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supporting information
p. 12990 - 12996
(2015/10/28)
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- Pd(0)/PR3-catalyzed intermolecular arylation of sp3 C-H bonds
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(Figure Presented) Pd(0)-catalyzed intermolecular arylation of sp 3 C-H bonds has been achieved using PR3/Arl. This protocol can be used to arylate a variety of aliphatic carboxylic acid derivatives, including a number of bioactive d
- Wasa, Masayuki,Engle, Keary M.,Yu, Jin-Quan
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supporting information; experimental part
p. 9886 - 9887
(2009/12/06)
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- Novel pyridine derivatives as potent and selective CB2 cannabinoid receptor agonists
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Replacement of the phenyl ring in our previous (morpholinomethyl)aniline carboxamide cannabinoid receptor ligands with a pyridine ring led to the discovery of a novel chemical series of CB2 ligands. Compound 3, that is, 2,2-dimethyl-N-(5-methyl-4-(morpholinomethyl)pyridin-2-yl)butanamide was identified as a potent and selective CB2 agonist exhibiting in vivo efficacy after oral administration in a rat model of neuropathic pain.
- Chu, Guo-Hua,Saeui, Christopher T.,Worm, Karin,Weaver, Damian G.,Goodman, Allan J.,Broadrup, Robert L.,Cassel, Joel A.,DeHaven, Robert N.,LaBuda, Christopher J.,Koblish, Michael,Brogdon, Bernice,Smith, Steve,Bourdonnec, Bertrand Le,Dolle, Roland E.
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scheme or table
p. 5931 - 5935
(2010/07/07)
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- N-heteroaromatic ion and iminium ion substituted cyanine dyes for use as fluorescence labels
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The present invention relates to iminium ion substituted cyanine dyes having a fluoresence absorbance of between about 500 and 900 nm, a reduced tendency to aggregate and enhanced photostability. The cyanine dyes of the present invention are represented by the formula STR1 wherein n is 0, 1, 2 or 3; m is 0, 1, 2 or 3; R1 and R2 are taken together to form an aromatic ring or a fused polycyclic aromatic ring; R3 and R4 are taken together to form an aromatic ring or a fused polycyclic aromatic ring; R5 and R6 are independently selected from the group consisting of (CH2)p X where p is 1-18 and X is a functional group that reacts with amino, hydroxyl and sulfhydryl nucleophiles; R7 and R8 are independently selected from the group consisting of hydrogen, C1-C10 alkyl groups and where R7 and R8 are taken together to form a five- or six- membered heterocyclic ring; R9 are each independently selected from the group consisting of hydrogen, alkyl and where more than one R9 are taken together to form a five- or six- membered ring; Y is selected from the group consisting of C(CH3)2, S, O and Se; and Z is selected from the group consisting of C(CH3)2, S, O and Se.
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- Isocyanates and their preparation using hypochlorous acid
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The present invention relates to a process for preparation of an isocyanate comprising (a) reacting an amide with an aqueous solution of hypochlorous acid in the presence of an water-immiscible organic solvent to produce an N-chloro amide; and (b) reacting said N-chloro amide with a base in the presence of a phase transfer catalyst and a water immiscible organic solvent to produce an isocyanate.
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- Aromatic dithio dianhydrides
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There are provided bis(thioether) aromatic dianhydrides and method for making these materials. A bisthiol in the presence of base, or bisthiol basic salt, can be reacted with a nitro- or halo-substituted phthalic compound, such as an anhydride or anhydride precursor. These aromatic dithiodianhydrides can be used to make polyimides and polyesters, and can be used as curing agents for epoxy resins.
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