- A phosphine-free iron complex-catalyzed synthesis of cycloalkanes: Via the borrowing hydrogen strategy
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Herein we report a diaminocyclopentadienone iron tricarbonyl complex catalyzed synthesis of substituted cyclopentane, cyclohexane and cycloheptane compounds using the borrowing hydrogen strategy in the presence of various substituted primary and secondary 1,n diols as alkylating reagents. Deuterium labeling experiments confirm that the diols were the hydride source in this cascade process. This journal is
- Bettoni, Léo,Gaillard, Sylvain,Renaud, Jean-Luc
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supporting information
p. 12909 - 12912
(2020/11/07)
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- DERIVATIVES OF RELEBACTAM AND USES THEREOF
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Derivatives of relebactam, therapeutic methods of using the derivatives of relebactam, particularly in combination with β-lactam antibiotics and pharmaceutical compositions thereof are disclosed. The derivatives of relebactam are suitable for oral administration.
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Paragraph 1429-1431
(2020/04/24)
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- A Spiroalkylation Method for the Stereoselective Construction of α-Quaternary Carbons and Its Application to the Total Synthesis of (R)-Puraquinonic Acid
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Cyclic α-quaternary carbon stereocenters were prepared from biselectrophillic substrates and an easily prepared chiral bicyclic sulfonyl lactam. This was achieved in two steps by spiroalkylation, employing biphasic reaction conditions with a phase-transfer catalyst, followed by reduction and alkylation with a series of alkyl halide electrophiles. The products of this method were isolated in good yields with with high levels of diastereoselectivity. This methodology was employed in the enantioselective total synthesis of (R)-puraquinonic acid (1) for a late-stage installation of the α-quaternary carbon stereocenter. This enabled the shortest synthesis of 1 to date, an eight-pot sequence providing an overall yield of 14%.
- Elmehriki, Adam A. H.,Gleason, James L.
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supporting information
p. 9729 - 9733
(2019/12/02)
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- AZTREONAM DERIVATIVES AND USES THEREOF
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Disclosed herein are aztreonam derivatives, therapeutic methods of using the aztreonam derivatives, particularly in combination with β-lactamase inhibitors, and pharmaceutical compositions thereof. The aztreonam derivatives can be administered orally to provide orally bioavailable aztreonam.
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Paragraph 0990; 0991; 1150; 1151
(2019/04/18)
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- Beta-lactamase inhibitors and uses thereof
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β-Lactamase inhibiting compounds, therapeutic methods of using the β-lactamase inhibiting compounds, particularly in combination with β-lactam antibiotics and pharmaceutical compositions thereof are disclosed. The β-lactamase inhibiting compounds are suitable for oral administration.
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Page/Page column 89
(2018/10/24)
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- A Palladium(II)-Catalyzed C-H Activation Cascade Sequence for Polyheterocycle Formation
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Polyheterocycles are found in many natural products and are useful moieties in functional materials and drug design. As part of a program towards the synthesis of Stemona alkaloids, a novel palladium(II)-catalyzed C-H activation strategy for the construction of such systems has been developed. Starting from simple 1,3-dienyl-substituted heterocycles, a large range of polycyclic systems containing pyrrole, indole, furan and thiophene moieties can be synthesized in a single step. Don't overdo it: A palladium(II)-catalyzed C-H activation cascade sequence for the synthesis of polyheterocycles is reported. Aromatization of the initially formed dihydro species occurred with a quinone oxidant. In some cases the use of one equivalent of the oxidant enabled isolation of the dihydro species as a single isomer (see scheme; X=NMe, O, S).
- Cooper, Stephen P.,Booker-Milburn, Kevin I.
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supporting information
p. 6496 - 6500
(2015/06/02)
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- NOVEL COMPOUNDS FOR MODULATION OF ROR-GAMMA ACTIVITY
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The present invention relates to aryl sulfones and related compounds that are modulators of ROR-gamma receptors. The invention also provides pharmaceutical compositions comprising these modulators, and methods of modulating ROR-gamma receptors using them. Also provided are methods of using aryl sulfones and related compounds as modulators of ROR-gamma to treat ROR-gamma mediated diseases
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Paragraph 00450
(2014/03/22)
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- Total synthesis of ceratopicanol through tandem cycloaddition reaction of a linear substrate
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Total synthesis of ceratopicanol (1) was achieved with a tandem cycloaddition reaction of allenyl diazo compound 6 via a trimethylenemethane (TMM) diyl intermediate. The TMM diyl mediated [2+3] cycloaddition reaction furnished the consecutive quaternary c
- Lee, Sang-Shin,Kim, Won-Yeob,Lee, Hee-Yoon
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p. 2450 - 2456,7
(2020/08/24)
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- METHODS, COMPOUNDS, AND COMPOSITIONS FOR DELIVERING 1,3-PROPAN ED ISULFONIC ACID
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The invention relates to methods, compounds, and compositions for delivering 1,3-propanedisulfonic acid (1,3PDS) in a subject, preferably a human subject. The invention encompasses compounds that will yield or generate 1,3PDS, either in vitro or in vivo. The invention also relates to sulfonate ester prodrugs of 1,3PDS as well as Gemini dimmers and oligomers of 1,3PDS for the prevention or treatment of associated diseases and conditions.
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Page/Page column 83
(2011/02/24)
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- Lipase-catalyzed regioselective monoacetylation of unsymmetrical 1,5-primary diols
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"Chemical Equation Presented" Lipase B from Candida antarctica (CALB) has been selected as the most suitable enzyme to catalyze the regioselective monoacetylation of 1,5-diol isoprostane intermediate, using vinyl acetate as an acyl transfer reagent in TIIF. We next applied this reaction on linear 2-substituted, 2,2′-disubstituted-l,5pentanediols, and, cyclic 2,3-disubstituted-l,5-pentanediols. To rationalize the regioselectivity observed, molecular docking simulations were performed.
- Oger, Camille,Marton, Zsuzsanna,Brinkmann, Yasmin,Burtel-Ponce, Valerie,Durand, Thierry,Graber, Marianne,Galano, Jean-Marie
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supporting information; experimental part
p. 1892 - 1897
(2010/05/19)
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- Intramolecular cyclopropanation of unsaturated terminal epoxides and chlorohydrins
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Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]-hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]-hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.
- Hodgson, David M.,Ying, Kit Chung,Nuzzo, Irene,Freixas, Gloria,Kulikiewicz, Krystyna K.,Cleator, Ed,Paris, Jean-Marc
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p. 4456 - 4462
(2008/02/02)
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- A new strategy for the synthesis of taurine derivatives using the 'safety-catch' principle for the protection of sulfonic acids
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The safety-catch principle has been applied for the development of a new method for protecting sulfonic acids. 2,2-Dimethylsuccinic acid was reduced to 2,2-dimethylbutane-1,4-diol, which was selectively silylated to give 4-(tert-butyldiphenylsilanyloxy)-2,2-dimethylbutan-1-ol. Reaction of the latter compound with 2-chloroethanesulfonyl chloride in the presence of triethylamine afforded 4-(tert-butyldiphenylsilyloxy)-2,2-dimethylbutyl ethenesulfonate directly. The ethenesulfonate underwent Michael-type addition with secondary amines to give protected derivatives of taurine (2-aminoethanesulfonic acid). Deprotection was achieved on treatment with tetrabutylammonium fluoride, whereby cleavage of the silicon-oxygen bond led to an intermediate alkoxide that immediately cyclised to 2,2-dimethyltetrahydrofuran with liberation of a sulfonate. Pure sulfonic acids were obtained from the crude product by ion exchange chromatography on a strongly basic resin, which was eluted with aqueous acetic acid. The method developed should be generally applicable to the protection of sulfonic acids and is amenable to a multiparallel format. This journal is The Royal Society of Chemistry.
- Seeberger, Sonja,Griffin, Roger J.,Hardcastle, Ian R.,Golding, Bernard T.
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p. 132 - 138
(2008/03/14)
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- PRODRUGS OF HIV PROTEASE INHIBITORS
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A compound of the formula , or is disclosed as a prodrug of an HIV protease inhibitor. Methods and compositions or inhibiting HIV protease activity and treating HIV infection are also disclosed.
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Page/Page column 78
(2010/10/19)
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- The regiochemistry of cyclization of α-sulfenyl-, α-sulfinyl-, and α-sulfonyl-5-hexenyl radicals: Procedures leading to regioselective syntheses of cyclic sulfones and sulfoxides
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A study of the cyclization of α-sulfenyl-, α-sulfinyl-, and α-sulfonyl-5-hexenyl and 5-methyl-5-hexenyl radicals reveals a unique contrast in the mode of ring closure of the radicals. In the case of the 5-hexenyl radicals, the sulfinyl-substituted species displays unexpected regioselectivity relative to its analogues. Thus, while the α-S- and α-SO2-5-hexenyl radicals give measurable and increasing quantities of 6-endo product, the α-sulfinyl species cyclizes with high selectivity (95.5:4.5) via a 5-exo mode. By contrast, ring closure of the 5-methyl-5-hexenyl radicals is found to give substantially the 6-endo product in all cases. It is the α-sulfonyl-5-methyl-5-hexenyl radical that now exhibits high regioselectivity (97.5:2.5) for 6-endo closure: an illustration of the synthetic value of this observation is the independent synthesis of the model cyclohexyl sulfone 61 in high yield. It is found that ring closure under the conditions employed occurs irreversibly in all cases.
- Della, Ernest W.,Graney, Sean D.
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p. 3824 - 3835
(2007/10/03)
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- Intramolecular Diels-Alder reactions using α-methylene lactones as dienophile
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Several dienals were prepared and reacted in the presence of zinc metal with ethyl 2-bromomethylacrylate to provide in a Reformatsky-like reaction α-methylene lactones carrying a dienyl side chain. Thermolysis of these compounds (11, 21, 29, and 37) gave in an intramolecular Diels-Alder reaction the corresponding tricyclic cycloadducts (51, 52, 53, and 54). The cycloadditions took place with good diastereoselectivity and yields. The stereochemistry of the major isomer is in accordance with an endo transition state for cycloadducts 51, 52, and 54. In one instance (compound 58), the structure was supported by X-ray crystallography. In contrast to the other substrates, the nonatriene 29 cyclized to the exo product 53exo. The stereochemical situation could also be proven by NOESY NMR. However, the intramolecular Diels-Alder reaction did not work with furan as dienophile (compound 41) and substrate 50 featuring a densely functionalized tether connecting diene and α-methylene lactone.
- Richter, Frank,Bauer, Matthias,Perez, Caroline,Maichle-Moessmer, Caecilia,Maier, Martin E.
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p. 2474 - 2480
(2007/10/03)
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- Synthesis of (3aR*,baR*)-2,2,5,6-tetramethyl-1,2,3,3a4,6a-hexahydropental ene: A potential precursor of protoilludane sesquiterpenes
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Acid-catalyzed rearrangement of 3,3,3',3'-tetramethyl-1,1'-bi(cyclobutylidene) (8) results in the formation of (3aR*,6aR*)-2,2,5,6-tetramethyl-1,2,3,3a,4,6a-hexahydropenta lene [(3aR*,6aR*)-9], a potential precursor of protoilludane sesquiterpenes. Compound 8 is prepared by oxidation and in situ coupling of cyclobutylidene-phosphorane 7.
- Fitjer,Gerke,Anger
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p. 893 - 894
(2007/10/02)
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- SELECTIVE OXIDATION OF A PRIMARY HYDROXYL IN THE PRESENCE OF SECONDARY ONE
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RuCl2(PPH3)3-benzene system has been found to be highly effective for the title selective oxidation providing 10-hydroxyundecanal in 89percent yield from 1,10-undecanediol.
- Tomioka, Hiroki,Takai, Kazuhiko,Oshima, Koichiro,Nozaki, Hitosi
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p. 1605 - 1608
(2007/10/02)
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