- Silylium-Ion-Promoted (5+1) Cycloaddition of Aryl-Substituted Vinylcyclopropanes and Hydrosilanes Involving Aryl Migration
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A transition-metal-free (5+1) cycloaddition of aryl-substituted vinylcyclopropanes (VCPs) and hydrosilanes to afford silacyclohexanes is reported. Catalytic amounts of the trityl cation initiate the reaction by hydride abstraction from the hydrosilane, and further progress of the reaction is maintained by self-regeneration of the silylium ions. The new reaction involves a [1,2] migration of an aryl group, eventually furnishing 4- rather than 3-aryl-substituted silacyclohexane derivatives as major products. Various control experiments and quantum-chemical calculations support a mechanistic picture where a silylium ion intramolecularly stabilized by a cyclopropane ring can either undergo a kinetically favored concerted [1,2] aryl migration/ring expansion or engage in a cyclopropane-to-cyclopropane rearrangement.
- Bonetti, Vittorio,He, Tao,Klare, Hendrik F. T.,Oestreich, Martin,Wang, Guoqiang
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supporting information
p. 12186 - 12191
(2020/05/22)
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- Br?nsted acid mediated intramolecular cyclopropane ring expansion/[4 + 2]-cycloaddition
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A cascade reaction of 3-hydroxy-2-phenylisoindolin-1-one and cyclopropyl ketone has been developed via a Br?nsted acid-promoted ring-opening/intramolecular cross-cycloaddition/[4 + 2]-cycloaddition process. The developed methodology provides straightforward access to pentacyclic isoindolin-1-one derivatives under simple reaction conditions.
- Li, Jian,Zhu, Shangrong,Xu, Qiuneng,Liu, Li,Yan, Shenghu
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p. 10004 - 10008
(2019/12/23)
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- Mild Ring Contractions of Cyclobutanols to Cyclopropyl Ketones via Hypervalent Iodine Oxidation
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An iodine-mediated oxidative ring contraction of cyclobutanols has been developed. The reaction allows the synthesis of a wide range of aryl cyclopropyl ketones under mild and eco-friendly conditions. A variety of functional groups including aromatic or alkyl halides, ethers, esters, ketones, alkenes, and even aldehydes are nicely tolerated in the reaction. This is in contrast with traditional synthetic approaches for which poor functional group tolerance is often a problem. The practicality of the method is also highlighted by the tunability of iodine oxidation system. Specifically, combining the iodine(III) reagent with an appropriate base allows the reaction to accommodate a range of challenging electron-rich arene substrates. The facile scalability of this reaction is also exhibited herein. (Figure presented.).
- Sun, Yan,Huang, Xin,Li, Xiaojin,Luo, Fan,Zhang, Lei,Chen, Mengyuan,Zheng, Shiya,Peng, Bo
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supporting information
p. 1082 - 1087
(2018/01/27)
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- Method for preparing 4-cypro methylene phenylboronic acid
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The invention discloses a method for preparing a 4-cypro methylene phenylboronic acid, and relates to the technical field of organic synthesis. The chlorobenzene is taken as the starting material, is subjected to a friedel-crafts reaction to generate 4-butanoyl chloride chlorobenzene, is subjected to a ring-closure reaction to generate 4-cypro formyl chlorobenzene, is subjected to a reduction reaction to generate 4-cypro methylene chlorobenzene, and is finally subjected to a Grignard boric acid reaction to generate the 4-cypro methylene phenylboronic acid. The cheap chlorobenzene, which is easy to get, is taken as the starting material, the preparation cost is remarkably lowered, the total molar yield of the product of 4-cypro methylene phenylboronic acid prepared through the 4-cypro methylene phenylboronic acid, the ring-closure reaction, the reduction reaction and the Grignard boric acid reaction is more than 35%, the production of the product is guaranteed on the basis of the low cost, and the method is suitable for industrial production.
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Paragraph 0027
(2017/08/31)
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- NOVEL CARBOCYCLIC COMPOUNDS AS ROR GAMMA MODULATORS
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The present disclosure is directed to novel carbocyclic compounds of formula (I) and pharmaceutically acceptable salts thereof, wherein R1, R2, R3, R4, R5, R6, Ra, Rb, n, m and p are as defined herein, which are active as modulators of retinoid-related orphan receptor gamma t (RORγt). These compounds prevent, inhibit, or suppress the action of RORγt and are therefore useful in the treatment of RORγt mediated diseases, disorders, syndromes or conditions such as, e.g., pain, inflammation, COPD, asthma, rheumatoid arthritis, colitis, multiple sclerosis, psoriasis, neurodegenerative diseases and cancer.
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Page/Page column 27; 41
(2017/03/21)
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- Solar photochemical oxidations of benzylic and allylic alcohols using catalytic organo-oxidation with DDQ: Application to lignin models
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Visible light has a dramatic effect on the oxidation of benzylic and allylic alcohols, including those deactivated by electron-withdrawing groups, and β-O-4 lignin models, using catalytic amounts of the organo-oxidant 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Sodium nitrite or tert-butyl nitrite is used as cocatalyst, and oxygen is employed as the terminal oxidant.
- Walsh, Katie,Sneddon, Helen F.,Moody, Christopher J.
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p. 5224 - 5227
(2014/12/11)
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- A cascade approach to fused indolizinones through Lewis acid-copper(i) relay catalysis
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A relay catalytic cascade process involving Lewis acid triggered ring-opening of cyclopropyl ketones with nitriles, the copper(i)-catalyzed Ritter process, and acid-promoted N-acyliminium ion cyclization is described, which efficiently provides thieno-, furano-, and benzo-indolizinones in moderate to good yields. The Royal Society of Chemistry 2013.
- Huang, Huawen,Ji, Xiaochen,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 3351 - 3353
(2013/06/04)
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- Asymmetric preparation of antifungal 1-(4′-chlorophenyl)-1- cyclopropyl methanol and 1-(4′-chlorophenyl)-2-phenylethanol. Study of the detoxification mechanism by Botrytis cinerea
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Chiral alcohols are important as bioactive compounds or as precursors to such molecules. On the basis of the different antifungal properties of the enantiopure alcohol derivatives of 4′-chlorophenyl cyclopropyl ketone and benzyl 4′-chlorophenyl ketone, their enantioselective synthesis by chemical and biocatalytic methods was studied. The detoxification pathways by the phytopathogen fungus Botrytis cinerea are reported.
- Pinedo-Rivilla, Cristina,Bustillo, Antonio J.,Hernandez-Galan, Rosario,Aleu, Josefina,Collado, Isidro G.
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experimental part
p. 61 - 66
(2012/02/03)
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- Preparation and reactivity of functionalized aryl and alkenylmanganese halides
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Various functionalized aryl and alkenyl manganese halides have been prepared from the corresponding aryl and alkenylhalides according to a one-pot procedure: lithium-halogen exchange at low temperature then Li-Mn transmetallation.
- Klement, Ingo,Stadtmueller, Heinz,Knochel, Paul,Cahiez, Gerard
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p. 1927 - 1930
(2007/10/03)
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- Insecticidal substituted-biphenylmethyl oxime ethers
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Oxime ethers of the formula STR1 wherein R1 is isopropyl, cyclopropyl, cyclopropylmethyl, or cyclobutyl; X and Y are independently halogen or straight or branched chain alkyl or alkoxy of 1 to 4 carbon atoms optionally substituted with one or more halogen atoms; n is 0-2; and m is 1-4 are disclosed. The insecticidal efficacy and preparation of the compounds are described and exemplified.
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- Optionally substituted phenyl-α-cyclopropyl acetic acid esters and use as insecticides
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New insecticides are of general formula: STR1 where R1, R2, R3, R4 and R5 represent H or methyl, R6 represents alkyl, alkoxy, halogeno or nitro or two R6 groups together represent methylenedioxy, and R is a group forming insecticidal esters with chrysanthemic acid such as 5-benzyl-3-furylmethyl, 3-phenoxybenzyl or α-cyano-3-phenoxybenzyl. They are prepared by esterification methods.
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