专利号:US-11370736-B2 优先权日:2019-04-01 标 题:Synthesis of fluoro hemiacetals via transition metal-catalyzed fluoro ester and carboxamide hydrogenation 发明人:DUB PAVEL A; BATRICE RAMI J; GORDON JOHN C 权利人:TRIAD NAT SECURITY LLC 摘要:This application is directed to use of transition metal-ligand complexes to hydrogenate fluorinated esters and carboxamides into fluorinated hemiacetals. Methods for synthesis of certain ligands are also provided.
专利号:US-2025011348-A1 优先权日:2023-06-13 标题:Synthesis Process of X-IPM, Stable Crystal Form and Application Thereof 发明人:DUAN JIANXIN; LU ZHAOQIANG; CAI XIAOHONG; FAN JINWEI; QIN WEI; HUANG QUNHUI; ZHANG YANJUN; CHEN WEISU 权利人:ASCENTAWITS PHARMACEUTICALS LTD 摘要:The present application relates to a new method for synthesizing isophosphoramide nitrogen mustard (X-IPM) that is suitable for industrialized production, involves fewer types of solvents, and leads to stable products with high yield. This method is charazterized mainly by the batchwise addition of M (e.g., M is R3N with R being ethyl; i.e., M is triethylamine) and the specific post-reaction treatment, which make it possible for the reaction to fully proceed, lead to products with less impurities, high yield and relatively stable properties, and can lead to stable crystallized substances with specific crystal structures. The present application also relates to stable crystal forms of the isophosphoramide nitrogen mustard (X-IPM) prepared by the aforementioned method, and use of the same as reactants for the synthesis of aziridine structure-containing compounds.
专利号:US-6423871-B1 优先权日:1999-02-26 标题 :Efficient synthesis of secondary amines by selective alkylation of primary amines 发明人:JUNG KYUNG WOON 权利人:UNIV SOUTH FLORIDA 摘要:A method for selective mono-N-alkylation of primary amines to produce secondary amines that are substantially free of overalkylated tertiary amines and quaternary ammonium salts, under mild reaction conditions without the necessity of protecting groups. Compounds of the class of secondary amines are produced by reacting an alkyl halide with an alkyl amine in anhydrous solvent, preferably dimethyl sulfoxide or N,N-dimethylformamide, in the presence of 0.1 to 3 molar equivalents of a cesium base. Optionally, the extent and selectivity of mono-N-alkylation is enhanced by addition to the reaction mixture of a powdered molecular sieve material for removal of water produced by the reaction, and/or tetrabutylammonium iodide to promote halide exchange. The invention permits selective and efficient mono-N-alkylation of a wide variety of substrates at 23° C.; does not cause racemization when used with enantiomerically-pure chiral substrates such as L-α-aminoesters; and is applied to solid phase synthesis whereby either the alkyl amine or alkyl halide is immobilized. The method is additionally used to produce polyamines, such as N-(2-(2-aminoethylthio)ethyl)ethylenediamine in 73% yield.
专利号:WO-0050377-A1 优先权日:1999-02-26 标 题:Efficient synthesis of secondary amines by selective alkylation of primary amines 发明人:JUNG KYUNG WOON 权利人:UNIV SOUTH FLORIDA 摘要:A method for selective mono-N-alkylation of primary amines to produce secondary amines that are substantially free of overalkylated tertiary amines and quaternary ammonium salts, under mild reaction conditions without the necessity of protecting groups. Compounds of the class of secondary amines are produced by reacting an alkyl halide with an alkyl amine in anhydrous solvent, preferably dimethyl sulfoxide or N,N-dimethylformamide, in the presence of 0.1 to 3 molar equivalents of a cesium base. Optionally, the extent and selectivity of mono-N-alkylation is enhanced by addition to the reaction mixture of a powdered molecular sieve material for removal of water produced by the reaction, and/or tetrabutylammonium iodide to promote halide exchange. The invention permits selective and efficient mono-N-alkylation of a wide variety of substrates at 23 °C; does not cause racemization when used with enantiomerically-pure chiral substrates such as L-α-aminoesters; and is applied to solid phase synthesis whereby either the alkyl amine or alkyl halide is immobilized. The method is additionally used to produce polyamines, such as N-(2-(2-aminoethylthio)ethyl)ethylenediamine in 73 % yield.
专利号:US-2025026871-A1 优先权日:2021-04-06 标 题:Cyclic ruthenium benzylidene initiators for enhanced ring expansion metathesis polymerization 发明人:GOLDER MATTHEW; WANG TENG-WEI; JOHNSON JEREMIAH A 权利人:UNIV WASHINGTON; MASSACHUSETTS INSTITUTE OF TECH M I T; MASSACHUSETTS INST TECHNOLOGY 摘要:Cyclic ruthenium benzylidene initiators useful for the controlled synthesis of functionalized cyclic macromolecules via ring-expansion metathesis polymerization.
专利号:US-10266503-B1 优先权日:2016-05-24 标 题 :Sulfoxide ligand metal catalyzed oxidation of olefins 发明人:WHITE M CHRISTINA; AMMANN STEPHEN E; LIU WEI; MA RULIN 权利人:UNIV ILLINOIS 摘要:The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee). Additionally, C(sp 3 )-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.
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合成参考文献
摘要:Yakugaku Zasshi. Journal of Pharmacy., 97(1117), 1977 []