72800-48-7Relevant articles and documents
One-Carbon Homologation of Primary Alcohols and the Reductive Homologation of Aldehydes Involving a Jocic-Type Reaction
Li, Zhexi,Gupta, Manoj K.,Snowden, Timothy S.
, p. 7009 - 7019 (2015/11/16)
(Trichloromethyl)carbinols, which are formed in one operation from either alcohols or aldehydes, can be converted into primary alcohols in a Jocic-type reaction involving LiBH4. The net result is a convenient two-step, one-carbon homologation of primary alcohols or a reductive one-carbon homologation of aldehydes featuring a broad substrate scope. The method is step-economical, and it nicely complements established one-carbon homologation strategies. (Trichloromethyl)carbinols, which are formed in one operation from either alcohols or aldehydes, can be converted into primary alcohols in a Jocic-type reaction involving LiBH4. The net result is a convenient two-step, one-carbon homologation of primary alcohols or a reductive one-carbon homologation of aldehydes featuring a broad substrate scope.
BRUTON'S TYROSINE KINASE INHIBITORS
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Page/Page column 178; 179, (2014/05/24)
Disclosed herein are compounds that form covalent bonds with Bruton's tyrosine kinase (BTK). Methods for the preparation of the compounds are disclosed. Also disclosed are pharmaceutical compositions that include the compounds. Methods of using the BTK inhibitors are disclosed, alone or in combination with other therapeutic agents, for the treatment of autoimmune diseases or conditions, heteroimmune diseases or conditions, cancer, including lymphoma, and inflammatory diseases or conditions. (Formula I)
One-pot synthesis of trichloromethyl carbinols from primary alcohols
Gupta, Manoj K.,Li, Zhexi,Snowden, Timothy S.
experimental part, p. 4854 - 4860 (2012/07/30)
Versatile trichloromethyl carbinols can be prepared in one pot from primary alcohols by treatment with Dess-Martin periodinane (DMP) in CHCl3 followed by introduction of commercially available 1,5,7-triazabicyclo[4.4.0] dec-5-ene (TBD). A modification of the method was used to convert chiral primary alcohol (R)-(-)-2,2-dimethyl-1,3-dioxolane-4-methanol to the corresponding trichloromethyl carbinol with complete stereochemical fidelity, despite the reactant proceeding through a base-sensitive aldehyde intermediate.
General and practical conversion of aldehydes to homologated carboxylic acids
Cafiero, Lauren R.,Snowden, Timothy S.
supporting information; experimental part, p. 3853 - 3856 (2009/07/01)
(Chemical Equation Presented) The reaction of aldehydes with trichloromethide followed by sodium borohydride or sodium phenylseleno(triethyl) borate under basic conditions affords homologated carboxylic acids in high yields. This operationally simple procedure provides a practical, efficient alternative to other homologation protocols. The approach is compatible with sensitive aldehydes including enals and enolizable aldehydes. It also offers convenient access to α-monodeuterated carboxylic acids.
Practical chemo-enzymatic process for the preparation of (1R,cis)-2-(2,2-dihaloethenyl)-3,3-dimethylcyclopropane carboxylic acids
Fishman, Ayelet,Kellner, Dorit,Ioffe, David,Shapiro, Evgeny
, p. 77 - 87 (2013/09/07)
A practical chemo-enzymatic process for the preparation of optically active (1R,cis)-2-(2,2-dichloro (or dibromo)ethenyl)-3,3-dimethylcyclopropane carboxylic acids (permethrinic or deltamethrinic acids) from racemic 1,1,1-trichloro-2-acetoxy-4-methyl-3-pentene is described. The key intermediate, enantiopure (R)-1,1,1-trichloro-2-hydroxy-4-methyl-3-pentene, is prepared by a lipase catalysed kinetic resolution of the racemic acetate. The reaction mixture, containing (R)-alcohol and the unreacted (S)-acetate, is directly acetylated by a haloacetyl halide, and the products are separated by distillation. The (S)-acetate is racemized, and the (R)-haloacetate is transformed to the corresponding glycinate hydrochloride, followed by diazotization to (R)-1,1,1-trichloro-4-methyl-3-penten-2-yl diazoacetate. The stereoselective carbenic dediazotization of the (R)-diazoacetate furnishes the optically active (1R,4R,5S)-6,6-dimethyl-4-trichloromethyl-3-oxobicyclo[3.2.0]hexan-2-one, which is transformed to the desired enantiopure (1R,cis)-permethrinic or deltamethrinic acid in high optical yield (>99% ee) and overall chemical yield of 10-15%.
Preparation of halogenated alcohols
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, (2008/06/13)
The invention provides an improved process for preparing halogenated alcohols of the formula CX1X2X3CH(OH)CH:C(CH3)2 (I, X1, X2, X3=halo) by reacting CX1X2X3H with 3-methylbut-2-en-1-al in the presence of a strong base and an inert solvent.
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
Tanaka, Hideo,Yamashita, Shiro,Yamanoue, Motoi,Torii, Sigeru
, p. 444 - 450 (2007/10/02)
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.
Fluoride Ion-Catalyzed Generation and Carbonyl Addition of α-Halo Carbanions Derived from α-Halo Organosilicon Compounds
Fujita, Makoto,Obayashi, Michio,Hiyama, Tamejiro
, p. 4135 - 4146 (2007/10/02)
The title carbanion species are generated from the corresponding α-haloorganosilicon compounds by the action of a catalytic amount of tris(diethylamino)sulfonium difluorotrimethylsilicate and are found to undergo addition to aldehyde carbonyl efficiently at ambient temperature.The synthetic potential of the reaction is demonstrated by application to the synthesis of some insecticides.
Electrochemical Reduction of Trichloroacetaldehyde-Olefin-Addition-Products
Voigtlaender, R.,Matschiner, H.,Krzeminski, Chr.,Biering, H.
, p. 649 - 654 (2007/10/02)
Trichloroacetaldehyde reacts with different olefins forming addition products.In most cases this reaction results in 1,1,1-trichloro-2-hydroxy compounds (2a-d).But also a different route of reaction is possible.Thus 2,3-dimethylbut-1-ene (1e) forms 4-trichloro-1,1,2-tetrahydroxyfurane (2e) and cyclohexene (1f) forms 3-trichloromethyl-2-oxabicyclo-2,2,2-octane (2f).All addition products are suitable starting materials for electrochemical conversions.In acidic electrolytes, on lead cathodes the electrochemical reduction results in a simultaneous cleavage of a C-Cl and a C-O bond to form the CH=CCl2-group (3a-f).In neutral electrolytes, on mercury cathodes, however, a reductive conversion of a CCl3-group to a CHCl2-group takes place (4c, 4f).
Chain Reactions Induced by Cathodic Reduction
Shono, Tatsuya,Kise, Naoki,Masuda, Mitsuharu,Suzumoto, Takeshi
, p. 2527 - 2533 (2007/10/02)
Cathodic reduction of a system comprising carbon tetrachloride, chloroform, and an aldehyde led to an effective anionic chain reaction.The best current efficiency observed was about 1*104 percent .Such a chain reaction is an effective synthetic method for 1,1,1-trichloro-2-alkanols.The reaction system consisting of methyl trichloroacetate, methyl dichloroacetate, and an aldehyde and several other systems also exhibited a similar pattern of chain reaction.
