- Copper(I)/Ligand-Catalyzed 5- endo Radical Cyclization-Aromatization of 2,2,2-Trichloroethyl Vinyl Ethers: Synthesis of 2,3-Difunctionalized 4-Chlorofurans
-
Copper(I)/ligand-catalyzed one pot synthesis of highly substituted 2,3-difunctionalized-4-chlorofurans has been reported. The reaction proceeds via a Cu(I)-catalyzed regioselective 5-endo-trig radical cyclization of 2,2,2-trichloroethyl vinyl ethers follo
- Ram, Ram N.,Gupta, Dharmendra Kumar,Soni, Vineet Kumar
-
-
Read Online
- Visible-Light-Mediated Z -Stereoselective Monoalkylation of β,β-Dichlorostyrenes by Photoredox/Nickel Dual Catalysis
-
Metal-catalyzed alkylation of 1,1-dihalovinyl moiety commonly suffers from both a lack of stereoselectivity and the overreaction leading to the dialkylation product. The methodology described herein features a new pathway to alkylate stereoselectively β,β-dichlorostyryl substrates to provide the Z -trisubstituted olefin only with fair to good yields. This cross-coupling reaction bears on the smooth and photoinduced formation of a C-centered radical that engages in a nickel-catalyzed organometallic cycle to form the key C sp2-C sp3bond.
- Abdellaoui, Mehdi,Millanvois, Alexandre,Levernier, Etienne,Ollivier, Cyril,Fensterbank, Louis
-
supporting information
p. 1513 - 1518
(2021/02/26)
-
- Stereoselective Synthesis of Vinylboronates by Rh-Catalyzed Borylation of Stereoisomeric Mixtures
-
The stereoselective preparation of vinylboronates via rhodium-catalyzed borylation of E/Z mixtures of vinyl actetates is described, and this method was also extended to synthesis of vinyldiboronates. These transformations feature high functional group compatibility and mild reaction conditions. Control experiments support a mechanism that involved a Rh-catalyzed borylation-isomerization sequence. The isomerization of (Z)-vinylboronates to (E)-isomers was also demonstrated.
- Li, Shenhuan,Li, Jie,Xia, Tianlai,Zhao, Wanxiang
-
p. 462 - 468
(2019/03/28)
-
- Cross-coupling reactivity of 1,1-dichloroalkenes under palladium catalysis: Domino synthesis of diarylalkynes
-
An efficient synthesis of diarylalkynes was achieved from the domino cross-coupling reaction of 1,1-dichloroalkenes with triarylbismuth reagents under palladium-catalyzed conditions. Under the established palladium protocol, 1,1-dichloroalkenes demonstrated hitherto unknown remarkable cross-coupling reactivity with organometallic triarylbismuth reagents to furnish functionalized diarylalkynes.
- Maddali, L. N. Rao,Meka, Suresh
-
supporting information
p. 4412 - 4418
(2018/03/21)
-
- A Robust One-Step Approach to Ynamides
-
A robust one-step synthetic strategy for ynamide with cheap and easily available stock chemicals vinyl dichlorides and electron deficient amides as the starting material is described. In the absence of transition-metal catalyst, the reaction proceeds under mild reaction conditions in open air and thus rendering a convenient operation. This strategy is not only suitable for both terminal and internal ynamide synthesis but also amenable for large-scale preparation. Broad substrate scopes with respect to vinyl dichloride as well as electron-deficient amide were observed.
- Tu, Yongliang,Zeng, Xianzhu,Wang, Hui,Zhao, Junfeng
-
supporting information
p. 280 - 283
(2018/01/17)
-
- Method for producing fluorine-containing olefin
-
A method for producing at least one compound selected from the group consisting of a compound represented by formula (10), a compound represented by formula (11), a compound represented by formula (12), and a compound represented by formula (13), by reacting a compound represented by formula (2) and a compound represented by formula (7) in the presence of at least one compound selected from the group consisting of a compound represented by formula (1), a compound represented by formula (3), a compound represented by formula (4), a compound represented by formula (8), and a compound represented by formula (9).
- -
-
Paragraph 0408; 0409; 0410; 0411; 0412
(2017/01/17)
-
- β-(Carbonatoxy)alkyl radicals: A new subset of β-(ester)alkyl radical fragmentation during copper(I)-mediated synthesis of 1,1-dichloro-1-alkenes
-
A new subset of β-(ester)alkyl radicals is presented. It is the first study on the chemistry of β-(alkoxycarbonyloxy)alkyl radicals that fill the gap in the spectrum of the migrating groups in β-(ester)alkyl radical reactions. The change from less nucleofugal (acetate) group to the more nucleofugal (carbonate) group in the spectrum of the migrating group changed the reaction path from rearrangement to fragmentation. This approach has been used for the synthesis of 1,1-dichloroalkenes in high yields. The formation of dichloroalkenes was accounted by the involvement of alkene radical cation and carbonate anion pair (a CIP) as a result of heterolysis of the CO bond of the carbonate at the β-position of the β-(alkoxycarbonyloxy)alkyl radical. The alkene radical cation was trapped by nucleophilic reaction with MeOH to form methyl ester.
- Ram, Ram N.,Tittal, Ram K.
-
p. 4342 - 4345
(2014/07/22)
-
- Pd0-Catalyzed carbonylation of 1,1-dichloro-1-alkenes, a new selective access to Z-α-chloroacrylates
-
A novel and fully chemo- and stereoselective three component strategy leading to Z-α-chloroacrylates by a Pd0-catalyzed reaction of CO (1 atm) with 1,1-dichloro-1-alkenes and various alcohols is disclosed. This catalytic approach compares favourably with the Wittig type strategies as α-chloroacrylates of pure Z configuration are obtained in high yield. The Royal Society of Chemistry.
- Arthuis, Martin,Lecup, Anne,Roulland, Emmanuel
-
supporting information; experimental part
p. 7810 - 7812
(2010/11/18)
-
- METHOD FOR MAKING BIARYL COMPOUNDS, COMPOUNDS MADE BY THE METHOD, AND METHOD FOR THEIR USE
-
Certain disclosed embodiments of the present invention concern a method for making biaryl compounds by combining a diene with a dienophile under reaction conditions that facilitate a Diels-Alder reaction. Certain embodiments are particularly directed to making a tetra-ortho-substituted biaryl compounds. The disclosed method may involve using novel dienes, dienophiles, or both. Similarly, certain of the biaryl compounds are novel compounds too. Additional disclosed embodiments concern a method for making useful compounds by first making a Diels-Alder adduct. The Diels-Alder adduct is then further modified or coupled to other compounds. The method can be used to make carbazoles, such as Siamenol. Disclosed biaryl compounds are useful for a number of applications, such as pharmacophores and organocatalysts.
- -
-
Page/Page column 45-46
(2009/01/23)
-
- Suzuki-Miyaura cross-coupling of 1,1-dichloro-1-alkenes with 9-alkyl-9-BBN
-
We addressed an unexplored application of the Suzuki-Miyaura protocol to the cross-coupling of 1,1-dichloro-1-alkenes with 9-alkyl-9-BBN. The use of bisphosphine ligands with a large P-Pd-P bite angle allowed us to synthesize Z-chlorinated internal alkenes in good yields resulting from a selective monocoupling process, a recurrent challenge with 1,1-dichloro-1-alkenes. Moreover, these monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.
- Liron, Frederic,Fosse, Celine,Pernolet, Alban,Roulland, Emmanuel
-
p. 2220 - 2223
(2007/10/03)
-
- The first example of tungsten-based carbene generation from WCl6 and atomic carbon and its use in olefin metathesis
-
We describe a new route for the synthesis of tungsten-based carbenes generated by the reaction of WCl6 with atomic carbon in a carbon arc reactor. The active species formed under these conditions, [W] = CCl2, was found to catalyze olefin metathesis reactions of 1-octene, 2-octene and 1-heptene. We also evaluated the mechanism of formation of [W] = CCl2 within the WCl6/C system at the DFT level.
- Düz, Bülent,Yüksel, Dilek,Ece, Abdulilah,Sevin, Fatma
-
p. 5167 - 5170
(2007/10/03)
-
- SmI2-mediated elimination reaction of trichloromethyl carbinols: A facile method to synthesize vinyl dichlorides
-
Samarium diiodide-mediated elimination reaction provides a simple and general method to synthesize vinyl dichlorides from trichloromethyl carbinols directly in good to excellent yields.
- Li, Jian,Xu, Xiaoliang,Zhang, Yongmin
-
p. 9349 - 9351
(2007/10/03)
-
- Reduction of trihalomethyl carbinols and their acetates, mesylates and tosylates by indium metal
-
A study of reduction of trihalomethyl carbinols and their derivatives by indium metal shows that while trichloromethyl carbinols produce a mixture of the corresponding dichloromethyl carbinol and vinylidene dichloride, the acetates, mesylates and tosylate
- Ranu, Brindaban C.,Samanta, Sampak,Das, Arijit
-
p. 5993 - 5995
(2007/10/03)
-
- Process for the preparation of cyclopropylacetylene
-
The present invention relates generally to novel methods for the preparation of cyclopropylacetylene which is an essential reagent in the asymmetric synthesis of (S)-6-chloro-4-cyclopropylethynyl-4-trifluoromethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one; a useful human immunodeficiency virus (HIV) reverse transcriptase inhibitor with superior anti-retroviral activity. In the process, for example, cyclopropane carboxaldehyde is alkylated to form 1,1,1-trichloro-2-cyclopropyl-ethanol; which in turn undergoes elimination to form 1,1-dichloro-2-cyclopropyl-ethene; which in turn undergoes elimination to form cyclopropyl acetylene.
- -
-
Page column 14, 15-16
(2008/06/13)
-
- Ukokinase inhibitors
-
Compounds having the formula are inhibitors of urokinase and are useful in the treatment of diseases in which urokinase plays a role. Also disclosed are urokinase-inhibiting compositions and a method of inhibiting urokinase in a mammal.
- -
-
-
- Conversion of aromatic aldehydes into 1-aryl-2,2-dichloroethenes
-
A new general one-pot preparative method for the synthesis of 1-aryl(hetaryl)-2,2-dichloroethenes from aldehydes was developed. The method involves successive conversions of the latter into hydrazones followed by treatment with carbon tetrachloride in the
- Nenajdenko,Shastin,Korotchenko,Balenkova
-
p. 1047 - 1050
(2007/10/03)
-
- A new and practical synthesis of vinyl dichlorides via a non-Wittig-type approach
-
A practical approach for the conversion of aldehydes to vinyl dichlorides has been developed. These are three-step, one-pot reactions involving the formation of trichlorocarbinol by treatment of aldehydes with trichloroacetic acid and sodium trichloroacetate followed by in situ protection and elimination reactions to form the desired vinyl dichlorides in 85 to 95% yields. (C) 2000 Dupont Pharmaceuticals Company.
- Wang, Zhe,Campagna, Silvio,Xu, Guoyou,Pierce, Michael E.,Fortunak, Joseph M.,Confalone, Pat N.
-
p. 4007 - 4009
(2007/10/03)
-
- A novel synthetic approach to dichlorostyrenes
-
We found that N-unsubstituted hydrazones of aromatic aldehydes can be easily converted to the corresponding 1,1-dichlorostyrenes in the reaction with carbon tetrachloride using copper (I) chloride as catalyst. Factors affecting the route of the reaction and yields of the products were investigated. A proposed mechanism for the reaction is discussed. (C) 2000 Published by Elsevier Science Ltd.
- Shastin,Korotchenko,Nenajdenko,Balenkova
-
p. 6557 - 6563
(2007/10/03)
-
- An improved synthesis of dichloroalkylphosphonates, chloroalkynes and terminal alkynes via diethyl dichloromethylphosphonate
-
Diethyl 1,1-dichloromethylphosphonate (2) was synthesised in good yield from the reduction of 1,1,1-trichloromethylphosphonate (1) with i-C3H7MgCl and subsequent hydrolysis. The reactivity of 2 towards α-alkylation and its utility in the synthesis of chloroalkynes and terminal alkynes was investigated.
- Carran, John,Waschbuesch, Rachel,Marinetti, Angela,Savignac, Philippe
-
p. 1494 - 1498
(2007/10/03)
-
- Generation of 2-Substituted 1-Ethenyl Cations from Ethylenediazonium Salts
-
Thermal decomposition of 2-substituted ethylenediazonium salts 1a-d produces the corresponding 1-ethenyl cations 2a-d as short-lived intermediates.The primary vinyl cation 2d or the rearranged and energetically favored analogues 3a-c of 2a-c are intercepted by chloride to give the decomposition products 4d and 5a-c, respectively.The generation of 4d and 5a-c as well as a kinetic study of the thermolysis reaction provide no indication that the elimination of nitrogen from 1a-d is occurring with the intermediate formation of cyclic cations 6 or 7. - Key Words: Ethylenediazonium salts, thermal stability of, thermal degradation of / Ethenyl cations, generation of, rearrangement of, interception of / Kinetics
- Bott, Kaspar
-
p. 933 - 940
(2007/10/02)
-
- Electrochemical Wittig reaction. Part I. Synthesis of gem-dichloroalkenes
-
Two-electron electrochemical reduction of trichloromethyl tris(dimethylamino)phosphonium tetrafluoroborate led to dichloromethylene tris(dimethylamino)phosphorane, which was reacted with an aromatic or aliphatic aldehyde, to give gem-dichloroalkenes in go
- Jubault, Philippe,Feasson, Christian,Collignon, Noel
-
p. 1001 - 1006
(2007/10/02)
-
- Reaction of Dichlorocarbene with Sterically Protected Phosphabutatriene. Formation of a Stable Dimethylenephosphirane
-
The reaction of dichlorocarbene with 4,4-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphabutatriene gave 2-dichloromethylene-3-diphenylmethylene-1-(2,4,6-tri-t-butylphenyl)-1-phosphirane via 2,2-dichloro-3-(2,2-diphenylethenylidene)-1-(2,4,6-tri-t-butylphenyl)-1-phosphirane. Keywords: dichlorocarbene; phosphabutatriene; phospharadialene; phosphirane; steric protection
- Toyota, Kozo,Yoshimura, Hideki,Uesugi, Takahiko,Yoshifuji, Masaaki
-
p. 6879 - 6882
(2007/10/02)
-
- SYNTHESIS AND CHEMISTRY OF DIALKYL- AND DIARYLTRICHLOROMETHYLPHOSPHINES
-
Dialkyltrichloromethylphosphines; diphenyltrichloro-methylphosphine; P-chloro-dialkyl-dichloromethylenephosphoranes; P-chloro-diphenyl-dichloromethylenephophorane; phosphonium salt; chlorination; dehydration; condensation.
- Majewski, Piotr
-
p. 185 - 194
(2007/10/02)
-
- A facile method for the preparation of 1,1-dichloroolefins using benzenesulfonyl chloride as a chlorenium ion source
-
Reaction of the lithio anion derived from diethyl methylphosphonate with benzenesulfonyl chloride gives directly the (diethylphosphoryl)dichloromethyllithium. In situ reaction with aldehydes or ketones gives in high yields of 1,1-dichloroolefins in a convenient one-pot procedure.
- Lee,Shin,Oh
-
p. 1657 - 1661
(2007/10/02)
-
- Simple synthesis of 2-alkenyl- and 2-aryl-substituted 1,1-dichloroethylenes from unsaturated aldehydes
-
A three-step synthesis has been proposed for the preparation of 2-alkenyl- and 2-aryl-1,1-dichloroethylenes, involving the conversion of an aldehyde to its acylal (or α-trichloromethylcarbinol), α-trichloromethylcarbinol acetate, and 2-substituted 1,1-dichloro-olefin. The best procedure for the dechloroacetoxylation by the action of zinc powder in a mixture of acetic acid and ether.
- Zhdankina,Kryshtal',Serebryakov,Yanovskaya
-
p. 2589 - 2591
(2007/10/02)
-
- Reductive Addition of Polyhalomethanes and Their Related Compounds to Aldehydes and 1,2-Elimination of the Coupling Products in a Pb/Al Bimetal Redox System
-
A Pb/Al bimetal system was used to carry out reductive addition of tetrachloromethane, tetrabromomethane, bromotrichloromethane, trichloroacetamide, and trichloroacetonitrile to aldehydes.Subsequent 1,2-elimination of the halogen atom and hydroxyl group from the coupling products was also performed with the Pb/Al bimetal system.The technology was successfully applied to stereocontrolled syntheses of ethyl trans- and cis-3-(2,2-dihaloethenyl)-2,2-dimethylcyclopropanecarboxylates.
- Tanaka, Hideo,Yamashita, Shiro,Yamanoue, Motoi,Torii, Sigeru
-
p. 444 - 450
(2007/10/02)
-
- Methoxide-induced fragmentation of 2,2,3-trihalogeno- and 2,2-dihalogeno-3-methoxy-1,3-diphenylpropanones
-
The reaction of 2,2,3-trihalogeno-1,3-diphenylpropanones with sodium methoxide in methanol occurs with exclusive formation of fragmentation products.Kinetic and stereochemical evidence is interpreted in terms of a concerted intramolecular process promoted by initial attack of methoxide anion at the carbonyl carbon.In the case of 2,2-dihalogeno-3-methoxy-1,3-diphenylpropanones the reaction gives fragmentation, rearrangement, and elimination products.The former products are believed to be formed through competing reactions involving an intermediate formed on addition of methoxide to the substrate.For the fragmentation pathway the results are consistent with a carbanionic-intermediate mechanism.
- Montani, Rosana S.,Garay, Raul O.,Cabaleiro, Mercedes C.
-
p. 1125 - 1130
(2007/10/02)
-
- Chromium(II) Reduction of Trichloromethyl Carbinols and their Corresponding Ethers: One-step Synthesis of Z-Vinyl Chlorides
-
Secondary trichloromethyl carbinols and their corresponding ethers can be reduced by chemically or electrochemically generated chromium(II) chloride to form Z-monochlorovinyl compounds in one step.In the presence of a carboxy function in the α-position an E-double bond is formed.Tertiary cabinols favour the formation of dichlorovinyl compounds and rearranged carbonyl compounds.Product ratios can be altered drastically by a change in the reaction conditions; this sheds light on the reaction mechanism.
- Wolf, Reinhard,Steckhan, Eberhard
-
p. 733 - 740
(2007/10/02)
-
- SYNTHESIS OF 2-ALKYLTHIO (OR TRIFLUOROMETHYLTHIO)-2-HALOGENOETHENYL DERIVATIVES BY MEANS OF WITTIG (UNDER PHASE TRANSFER CONDITIONS) OR WITTIG-HORNER REACTIONS. APPLICATION IN THE FIELD OF PYRETHROIDS.
-
A mixture of RSCHCl2, Ph3P and trans-caronaldehyde ethyl ester, treated with aq.NaOH under phase transfer conditions, gave the corresponding 2-alkylthio, 2-chloroethenyl derivative, the product of the Wittig reaction of a phosphorane
- Palla, Ottorino,Gozzo, Franco,Scaglioni, Leonardo
-
p. 1523 - 1532
(2007/10/02)
-
- Triazolothiadiazole 1-oxide: a New Fused Heterocyclic System from Dichlorosulphine and Aryldiazomethanes
-
2,7-Diaryltriazolothiadiazole 1-oxides can be obtained in a simple reaction from dichlorosulphine and aryldiazomethanes.The reaction consists of two successive cycloaddition steps, each of which is followed by elimination of hydrogen
- Bonini, Bianca F.,Maccagnani, Gaetano,Mazzanti, Germana,Zani, Paolo,Macciantelli, Dante
-
p. 1701 - 1708
(2007/10/02)
-
- Preparation of Alkyl Chlorides, Acid Chlorides, and Amides Using Polymer-Supported Phosphines and Carbon Tetrachloride: Mechanism of These Reactions
-
Alcohols and thiols were converted into alkyl chlorides, carboxylic acids were converted into acid chlorides, and mixtures of carboxylic acids and amines were converted into amides by reaction with carbon tetrachloride and 1percent cross-linked polystyrenes containing phosphine residues.Some of these conversions were also effected by using a linear polymer containing phosphine residues.The reactions proceed in high yield, and isolation of the products is facilitated by the ready removal of all the polymer-supported species.The mechanism of the reactions between triphenylphosphine, carbon tetrachloride, and alcohols is complex, but the polymer-supported reactions appear to follow analogous pathways to the low molecular weight reactions as judged by the yields of chloroform and the number of equivalents of phosphine consumed per mole of alkyl chloride produced.The mechanism requires polymer-supported groups reacting together.The slow step in the reactions appears to be the generation of the chlorinating species.The polymer-supported reactions are faster than those using triphenylphosphine or 4-(diphenylphosphinyl)isopropylbenzene.It is suggested that this is due to a microenvironmental effect.
- Harrison, Charles R.,Hodge, Philip,Hunt, Barry J.,Khoshdel, Ezzatollah,Richardson, Graham
-
p. 3721 - 3728
(2007/10/02)
-
- A CONVENIENT AND NOVEL SYNTHESIS OF 1,1-DICHLOROALKENES USING α-LITHIATED DICHLOROMETHYLTRIMETHYLSILANE AND ALDEHYDES
-
Various 1,1-dichloroalkenes can be prepared by the reaction of α-lithiated dichloromethyltrimethylsilane with aldehydes followed by hydrolysis.
- Hosomi, Akira,Inaba, Masahiro,Sakurai, Hideki
-
p. 4727 - 4728
(2007/10/02)
-
- The electrochemical Wittig-Horner reaction; evidence of a stepwise cleavage of a four-membered ring Wittig intermediate
-
Electro-reduction of diethyl(trichloromethyl)phosphonate in the presence of aldehydes or ketones relpaces the oxygen atom of the carbonyl group by a dichloromethylene group.The yield of 1,1-dichloroethene product decreases subtantially if the carbonyl com
- Tilborg, W. J. M. van,Smit, C. J.
-
p. 202 - 206
(2007/10/02)
-