- Method for preparing 3-chloro-2,2-dimethylpropionyl chloride
-
The invention discloses a method for preparing 3-chloro-2,2-dimethylpropionyl chloride. The method is characterized in that 3-chloro-2,2-dimethylpropioric acid and phosgene undergo an acylating chlorination reaction in the presence of a catalyst to obtain the 3-chloro-2,2-dimethylpropionyl chloride. The method has the advantages of simple process, easiness in operation, mild and easily-controlledconditions, low energy consumption, low cost, high yield, high purity, clean reaction, no pollution, realization of comprehensive utilization of a byproduct hydrochloric acid, and suitableness for industrial production.
- -
-
Paragraph 0031-0034; 0035; 0036; 0037-0050; 0051; 0052
(2018/11/04)
-
- Palladium-catalyzed C(carbonyl)-C bond cleavage of amides: a facile access to phenylcarbamate derivatives with alcohols
-
A sulfur-containing auxiliary enabled palladium-catalyzed C(carbonyl)-C bond activation of amides was reported to form phenylcarbamate derivatives with alcohols. Both alkyl and benzyl alcohols could be employed well with yields up to 85%. Derivations from phenylcarbamates to ureas and thiocarbamates illustrated the potential applications of this sequential C-C cleavage/C-O coupling reaction.
- Yan, Xufei,Sun, Huihui,Xiang, Haifeng,Yu, Da-Gang,Luo, Daibing,Zhou, Xiangge
-
supporting information
p. 8606 - 8609
(2018/08/06)
-
- Cu-Catalyzed Alkynylation of Unactivated C(sp3)-X Bonds with Terminal Alkynes through Directing Strategy
-
In this letter, we report an efficient and concise protocol for Cu-catalyzed cross-coupling of unactivated alkyl halides/peusudohalides with terminal alkynes to afford internal alkynes with the assistance of various amides as directing groups. Different alkyl halides/pseudohalides exhibited excellent reactivities, and the inactivated alkyl chlorides and sulfonates showed better reactivity than bromides/iodides. This is the first successful example to apply alkyl chlorides and sulfonates directly in cross-coupling with terminal alkynes in the absence of any additives. A Cu catalyst was found to be more effective than other transition metal catalysts. This reaction also exhibited a broad substrate scope with respect to terminal alkynes.
- Luo, Fei-Xian,Xu, Xing,Wang, Ding,Cao, Zhi-Chao,Zhang, Yun-Fei,Shi, Zhang-Jie
-
supporting information
p. 2040 - 2043
(2016/06/01)
-
- Reductive synthesis of aminal radicals for carbon-carbon bond formation
-
Aminal radicals were generated by reduction of the corresponding amidine or amidinium ion. The intermediate radicals participate in C-C bond-forming reactions to produce fully substituted aminal stereocenters. No toxic additives or reagents are required. More than 30 substrate combinations are reported, and chemical yields are as high as 99%.
- Schiedler, David A.,Lu, Yi,Beaudry, Christopher M.
-
supporting information
p. 1160 - 1163
(2014/03/21)
-
- Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp3)-H bonds
-
The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp3 C-H bond functionalization process. The reaction favors predominantly the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds. Moreover, a preference for activating sp3 C-H bonds of β-methyl groups, via a five-membered ring intermediate, over the aromatic sp2 C-H bonds was also observed in the cyclometalation step. Additionally, sp3 C-H bonds of unactivated secondary sp3 C-H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. Getting ahead on tams: The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp 3 C-H bond functionalization process to deliver β-lactams. The reaction favors the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds, as well as aromatic C(sp2)-H bonds and unactivated secondary C(sp3)-H bonds of rings.
- Wu, Xuesong,Zhao, Yan,Zhang, Guangwu,Ge, Haibo
-
supporting information
p. 3706 - 3710
(2014/04/17)
-
- Inhibitors of CYP 17
-
The present invention provides compounds of Formula (I) and (II), or a pharmaceutically acceptable salts thereof, where R53, R54, p, q, and n are as defined herein. The compounds of the present invention have been found to be useful as 17α-hydroxylase/C17,20-lyase inhibitors.
- -
-
Page/Page column 64
(2011/01/05)
-
- 1, 3-DISUBSTITUTED IMIDAZOLIDIN-2-ONE DERIVATIVES AS INHIBITORS OF CYP 17
-
The present invention provides compounds of Formula (I) and (II), or a pharmaceutically acceptable salts thereof, where R53, R54, p, q and n are as defined herein. The compounds of the present invention have been found to be useful as 17α-hydroxylase/C17,20-lyase inhibitors.
- -
-
Page/Page column 165; 210-211
(2011/01/12)
-
- Converting gem-dimethyl groups into cyclopropanes via Pd-catalyzed sequential C-H activation and radical cyclization
-
(Diagram presented) A novel route to the synthesis of cyclopropane derivatives is described. 1,1-Dimethyls in 2-(1,1-dimethylalkyl) dimethyloxazolines are first converted into 1,3-diiodide derivatives via Pd-catalyzed sequential C-H activation and then radically cyclized to provide 2-(1-alkylcylclopropyl)-dimethyloxazolines. The use of EtOAc as a solvent is crucial for the diiodination of the functionalized substrates.
- Giri, Ramesh,Wasa, Masayuki,Breazzano, Steven P.,Yu, Jin-Quan
-
p. 5685 - 5688
(2007/10/03)
-
- CATALYTICS ASYMMETRIC ACTIVATION OF UNACTIVATED C-H BONDS, AND COMPOUNDS RELATED THERETO
-
One aspect of the present invention is directed in part to catalytic and stereoselective functionalization of unactivated C-H bonds of simple organic substrates. The compounds and methods provided herein allow one to control the stereochemistry in a C-H activation step, activate substrates containing α-hydrogens next to the directing group, and remove a directing group under mild conditions. One aspect of the present invention relates to a transition-metal-catalyzed method for selective and asymmetric oxidation of carbons located in a β- or γ-position relative to an auxiliary. Another aspect of the invention relates to the enantiomerically-enriched substrates and the enantiomerically-enriched products formed via said method. In certain embodiments, oxazoline and oxazinone directing groups are used. In addition, the Boc protecting group has been identified as a directing group which does not necessitate removal.
- -
-
Page/Page column 90-91
(2010/10/20)
-
- Process for preparing acid halides
-
Acid halides of the formula (R1, R2, R3)C--CO--Hal are obtained by reacting alkyl halides of the formula (R1, R2, R3)C--Hal with carbon monoxide under a pressure of 5 to 1,000 bar and at a temperature of -20° C. to +100° C. in the presence of 0.001 to 0.3 mol of AlCl3 and/or FeCl3, if appropriate in the presence of a further Bronsted or Lewis acid, per mol of the alkyl halide. The process is carried out, if desired in the presence of a solvent which is customary for Friedel-Crafts or Friedel-Crafts-related reactions and, if appropriate in the presence of a hydrogen halide. The acid chloride can be isolated from the reaction mixture or further reacted.
- -
-
-
- CARBONYLATION OF TERTIARY ALKYL HALIDES, SYNTHESIS OF PIVALOYL HALIDES
-
The carbonylation of tert-butyl halides in a two-phase system, RSO3H/CCl4, under carbon monoxide pressure affords the corresponding pivaloyl halides in good yields and selectivities.
- Brunet, J.-J.,Legars, P.,Peres, Y.,Tkatchenko, I.,Lecolier, S.
-
p. 4569 - 4572
(2007/10/02)
-
- REGIOSELECTIVE CHLORINATION OF VALINE DERIVATIVES
-
Reaction of N-benzoylvaline methyl ester (5a) with sulphuryl chloride gave the β-chlorovaline derivative (6a) and lesser amounts of diastereoisomers of the γ-chlorovaline derivative (7a).A similar mixture of products was obtained throuch photolysis of the N-chloroamide (13).The reactions of the valine derivatives (5a) and (13) involve regioselective intermolecular transfer of the β-valinyl hydrogen.There is no evidence for reaction at the α-position.The β-chloroalanine derivative (23) was produced through reaction of N-benzoylalanine methyl ester (17a) with sulphuryl chloride and by photolysis of the N-chloroamide (22).Chlorination of the azetidinone (16a) gave (16b) in modest yield.These reactions establish the chemical validity of a regiospecific hydrogen-atom abstraction proposed in penicillin biosynthesis.
- Bowman, Nigel J.,Hay, Michael P.,Love, Stephen G.,Easton, Christopher J.
-
p. 259 - 264
(2007/10/02)
-
- Herbicidal 3-isoxazolidinones and hydroxamic acids
-
Novel 3-isoxazolidinone compounds and novel hydroxamic acid intermediates from which they are prepared exhibit herbicidal activity to grassy and broad-leaf plant species while leaving legumes, especially soybeans, unaffected. The preparation and herbicidal activity of the compounds is exemplified.
- -
-
-
- Convenient Syntheses of Cyclic Carboxamides from α,β,γ,δ and ε-halocarboxamides under Phase Transfer Conditions
-
Piperazine-2,5-diones (2) were prepared by N-alkylation between two molecules of α-halocarboxamides (1) in the presence of a phase transfer catalyst in yields of 64-88percent. β,γ,δ and ε-Lactams (6,9 and 13) were similarly synthesized by intramolecular N-alkylation of the corresponding halocarboxamides (5, 8 and 12) under phase transfer conditions in 53-99percent yields.Keywords--piperazine-2,5-dione; β-lactam; γ, δ, and ε lactams; bis-β-lactam; phase transfer catalyst; intramolecular N-alkylation
- Okawara, Tadashi,Matsuda, Takashi,Furukawa, Mitsuru
-
p. 1225 - 1233
(2007/10/02)
-
- Cytidine nucleoside compound
-
5'-Esters of ara-cytidine (1-β-D-arabinofuranosylcytosine) are prepared by reacting ara-cytidine with β,β,β-trihaloethoxycarbonyl halide or other protective agency to form a protective amido group on the primary amino nitrogen of ara-cytidine and then reacting the thus-protected compound with a reagent reactive with the 5'-O-hydroxyl group, e.g., an acylating agent, to form the 5'-O-derivative. The β,β,β-trihaloethoxycarbonyl or other protective group is then removed. Alternately, the primary amino group of ara-cytidine can be protected from acylation by protonation. The 5'-O-derivatives in their free base of salt form are characterized in that they display the property of sustained release of the compound, ara-cytidine, when administered intramuscularly or subcutaneously. Ara-cytidine is known for its anti-viral action and for its usefulness as an agent for controlling leukemias, including acute leukemia, and the sustained release property extends the usefulness of ara-cytidine for these purposes and as an inmunosuppressive agent. The 5'-O-derivartives of this invention can also be administered orally.
- -
-
-
