- A new polymorph of triphenyl-methyl-amine: The effect of hydrogen bonding
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Crystallization of the hexane reaction mixture after treatment of LiGe(OCH2CH2NMe2)3 with PH3CN 3 gives rise to a new triclinic (space group P ) polymorph of triphenyl-methyl-amine, Cl9H17N, (I), cont
- Khrustalev, Victor N.,Borisova, Irina V.,Zemlyansky, Nikolai N.,Antipin, M. Yu.
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- Copper catalyzed reduction of azides with diboron under mild conditions
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We report herein the first Cu catalyzed reduction of azides with B2pin2 (pin = pinacolato) as the reductant under very mild conditions. A series of primary amines and amides were obtained in moderate to excellent yields with high chemoselectivity and good functional group tolerance. This reaction can be performed with a cheap copper salt, a simple NHC ligand and a diboron reagent.
- Chen, Yang,Deng, Shengqi,Gao, Yihua,Liu, Liwen,Liu, Yu,Lu, Da,Wang, Qianwen,Zhang, Xiao
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supporting information
(2020/02/27)
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- Synthetic method of 3-hydroxyazetidine hydrochloride
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The invention discloses a synthetic method of 3-hydroxyazetidine hydrochloride, and belongs to the field of pharmacy. The synthetic method of the 3-hydroxyazetidine hydrochloride comprises the following steps: introducing hydrogen chloride gas into a solution formed by N-(triphenylmethyl)-3-hydroxyazetidine and a first organic solvent to carry out a reaction of removing triphenylchloromethane, andcarrying out solid-liquid separation to obtain the 3-hydroxyazetidine hydrochloride. The period for preparing the 3-hydroxyazetidine hydrochloride by utilizing the synthesis method is short, the safety is good, the use of toxic or expensive reagents is avoided, the reaction yield is high, the 3-hydroxyazetidine hydrochloride with high quality purity can be obtained, the operation is simple and convenient, and the method is suitable for large-scale industrial production.
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Paragraph 0065-0069
(2020/11/05)
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- Structure-based design, synthesis, and evaluation of the biological activity of novel phosphoroorganic small molecule IAP antagonists
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One of the strategies employed by novel anticancer therapies is to put the process of apoptosis back on track by blocking the interaction between inhibitor of apoptosis proteins (IAPs) and caspases. The activity of caspases is modulated by the caspases themselves in a caspase/procaspase proteolytic cascade and by their interaction with IAPs. Caspases can be released from the inhibitory influence of IAPs by proapoptotic proteins such as secondary mitochondrial activator of caspases (Smac) that share an IAP binding motif (IBM). The main purpose of the present study was the design and synthesis of phosphorus-based peptidyl antagonists of IAPs that mimic the endogenous Smac protein, which blocks the interaction between IAPs and caspases. Based on the structure of the IAP antagonist and recently reported thiadiazole derivatives, we designed and evaluated the biochemical properties of a series of phosphonic peptides bearing the N-Me-Ala-Val/Chg-Pro-OH motif (Chg: cyclohexylglycine). The ability of the obtained compounds to interact with the binding groove of the X-linked inhibitor of apoptosis protein baculovirus inhibitor of apoptosis protein repeat (XIAP BIR3) domain was examined by a fluorescence polarization assay, while their potential to induce autoubiquitination followed by proteasomal degradation of cellular IAP1 was examined using the MDA-MB-231 breast cancer cell line. The highest potency against BIR3 was observed among peptides containing C-terminal phosphonic phenylalanine analogs, which displayed nanomolar Ki values. Their antiproliferative potential as well as their proapoptotic action, manifested by an increase in caspase-3 activity, was examined using various cell lines.
- ?upicka-S?owik, Agnieszka,Psurski, Mateusz,Grzywa, Renata,Cuprych, Monika,Ciekot, Jaros?aw,Goldeman, Waldemar,Wojaczyńska, El?bieta,Wojaczyński, Jacek,Oleksyszyn, Józef,Sieńczyk, Marcin
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p. 1350 - 1364
(2020/04/24)
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- Isoselective Lactide Ring Opening Polymerisation using [2]Rotaxane Catalysts
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Polylactide (PLA) is a fully biodegradable and recyclable plastic, produced from a bio-derived monomer: it is a circular economy plastic. Its properties depend upon its stereochemistry and isotactic PLA shows superior thermal-mechanical performances. Here, a new means to control tacticity by exploiting rotaxane conformational dynamism is described. Dynamic achiral [2]rotaxanes can show high isoselectivity (Pi=0.8, 298 K) without requiring any chiral additives and enchain by a chain end control mechanism. The organocatalytic dynamic stereoselectivity is likely applicable to other small-molecule and polymerization catalyses.
- Lim, Jason Y. C.,Yuntawattana, Nattawut,Beer, Paul D.,Williams, Charlotte K.
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supporting information
p. 6007 - 6011
(2019/04/03)
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- Self-propagated Lossen rearrangement induced by a catalytic amount of activating agents under mild conditions
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A mild self-propagated Lossen rearrangement induced by a catalytic amount of activating agents in medium to high polar organic solvents has been developed. The rearrangement of aromatic and aliphatic hydroxamic acids in the presence of a catalytic amount (0.01 equiv) of acetic anhydride and an equimolar amount of base such as well-dried potassium carbonate afforded the corresponding amines in high yields. This alternative to traditional Lossen rearrangement provides a simple and mild method for the synthesis of amines from free hydroxamic acids.
- Hoshino, Yujiro,Shimbo, Yuki,Ohtsuka, Naoya,Honda, Kiyoshi
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supporting information
p. 710 - 712
(2015/01/30)
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- A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: Catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations
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A CuI catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI=NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C=C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.
- Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Chi, Lingyu,Wang, Qiuwen,Choudhury, Amitava,Mathieson, Jennifer S.,Cronin, Leroy,Pardue, Daniel B.,Cundari, Thomas R.,Mitrikas, George,Sanakis, Yiannis,Stavropoulos, Pericles
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supporting information
p. 11362 - 11381
(2014/09/17)
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- Tritylamine (triphenylmethylamine) in organic synthesis; III. The synthesis of 1-aminoalkylphosphonic acids in the reaction of N-(triphenylmethyl) alkanimines with phosphorus trichloride in acetic acid or with phosphonic (phosphorous) acid in acetic anhydride
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The reaction of phosphorus trichloride in acetic acid or phosphonic (phosphorous) acid in acetic anhydride, with N-(triphenylmethyl)alkanimines gives 1-acetylaminoalkylphosphonic acids 1a-j, which after hydrolysis give 1-aminoalkylphosphonic acids 2a-j in good yields. ARKAT USA, Inc.
- Goldeman, Waldemar,Soroka, Miroslaw
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experimental part
p. 360 - 369
(2011/02/27)
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- Rapid Ti(Oi-Pr)4 facilitated synthesis of α,α,α-trisubstituted primary amines by the addition of Grignard reagents to nitriles under microwave heating conditions
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A series of carbinamines (α,α,α-trisubstituted amines) have been prepared in a simple and efficient one-pot procedure by the addition of Grignard reagents to a series of aliphatic, aromatic and heteroaromatic nitriles. The resulting magnesium imines are subsequently converted to the desired amine after treatment with Ti(Oi-Pr)4 and additional microwave heating. Key to this procedure is the use of microwave heating for both steps of the reaction protocol, which significantly improves both reaction yields and reduces reaction times. In general, the Grignard addition reaction is complete within 5-10 min at 100 °C followed by conversion with Ti(Oi-Pr)4 and additional microwave heating to give the target amines in good yields.
- Wang, Ruifang,Gregg, Brian T.,Zhang, Wei,Golden, Kathryn C.,Quinn, John F.,Cui, Peng,Tymoshenko, Dmytro O.
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experimental part
p. 7070 - 7073
(2010/03/01)
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- One-pot synthesis of primary tert-alkylamines by the addition of organometallic reagents to nitriles mediated by Ti(Oi-Pr)4
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A number of primary tert-alkylamines (18 examples, 25-72% yields) have been prepared according to a simple one-pot procedure by the addition of organometallic reagents such as Grignard reagents and organolithium compounds to nitriles in the presence of Ti(Oi-Pr)4. Georg Thieme Verlag Stuttgart.
- Tomashenko, Olesya,Sokolov, Viktor,Tomashevskiy, Alexander,De Meijere, Armin
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p. 652 - 654
(2007/10/03)
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- Addition of organometallic reagents to nitriles promoted by titanium(IV) isopropoxide as a procedure of synthesis of primary tert-alkylamines
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Grignard reagents are able to add twice to nitriles in the presence of titanium(IV) isopropoxide providing primary tert-alkylamines in a fair yield. The conditions and structural features of reagents required for successful reaction were established. A po
- Tomashenko,Sokolov,Tomashevskii,Potekhin,De Meijere
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p. 1421 - 1426
(2008/09/16)
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- A convenient method for the preparation of primary amines using tritylamine
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A simple method for the preparation of primary amines by treating N-tritylamines with trifluoroacetic acid has been established. The N-tritylamines were prepared by the reaction of alkyl halides or alkyl p-toluenesulfonates with tritylamine, or by the reaction of alkyl bromides with lithium tritylamide.
- Theodorou, Vassiliki,Ragoussis, Valentine,Strongilos, Alexandros,Zelepos, Evangelos,Eleftheriou, Argyro,Dimitriou, Maria
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p. 1357 - 1360
(2007/10/03)
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- Preparations, X-ray crystal structure determinations, and base strength measurements of substituted tritylamines
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A range of tritylamines TrNRR′, and 4-methoxy-, 4,4′-dimethoxy-, and 4,4′,4″-trimethoxy-substituted analogues, have been prepared from (substituted) trityl chloride, bromide, or tetrafluoroborate with ammonia or with amines HNRR′ where R and R′ are hydrog
- Canle, Moises L.,Clegg, William,Demirtas, Ibrahim,Elsegood, Mark R.J.,Maskill, Howard
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- Process for the preparation of tertiary carbinamines
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This invention relates to a novel process for the preparation of tertiary carbinamines by double addition of organolanthanide reagents, especially organocerium reagents, to nitriles. It further relates to the preparation of such amines by the addition of
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- Tertiary Carbinamines by Addition of Organocerium Reagents to Nitriles and Ketimines
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Organocerium reagents, prepared by reaction of aromatic and primary and secondary alkyllithium reagents with anhydrous cerium chloride, add to nitriles twice to give tertiary carbinamines in often excellent yields.Addition of n-BuCeCl2 to acetophenone is about 4 times faster than addition to benzonitrile.Only 1,2-diaddition is observed in the reaction of MeCeCl2 with cinnamonitrile.The species formed in the double addition of organocerium reagents to nitriles are sufficiently basic to generate a benzyne intermediate by abstraction of an aromatic proton and nucleophilic enough to undergo an intramolecular Chichibabin reaction.Reaction of N-unsubstituted ketimines or their lithium salts with organocerium reagents permits the synthesis of tertiary carbinamines with three different groups on the tertiary carbon center.
- Ciganek, Engelbert
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p. 4521 - 4527
(2007/10/02)
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- A CHEMOSELECTIVE CONVERSION OF ALKYL AND ARYL AZIDES TO AMINES WITH SODIUM HYDROGENTELLURIDE
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By treatment with sodium hydrogentelluride in ethanol/ether at room temperature, alkyl and aryl azides are easily converted to the corresponding primary amines in good yields.
- Suzuki, Hitomi,Takaoka, Koji
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p. 1733 - 1736
(2007/10/02)
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- Studies on the Preparation and Reactions of Tritylsulfenimines
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Carbonyl compounds react with stable, crystalline triphenylmethanesulfenamide (TrSNH2, 4) under mild conditions to form tritylsulfenimines 5 and 6.Lithiation of acetone tritylsulfenimine (5c) at O deg C led to a novel rearrangement-decomposition producing
- Branchaud, Bruce P.
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p. 3531 - 3538
(2007/10/02)
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- The Protecting-Directing Role of the Trityl Group in Syntheses of Pyrrole Derivatives: Efficient Preparations of 1-H-Pyrrole-3-carboxylic Acid and 3-Acyl, 3-Amino, and 3-Bromo-1-tritylpyrroles
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Trifluoroacetylation, formylation, and bromination of 1-tritylpyrrile occur regioselectively at the 3-position in high yields.Quantitative hydrolysis of the 3-trifluoroacetyl derivative and removal of the trityl group from the resulting acid with sodium in liquid ammonia furnishes a new, short, high-yielding synthessis of the simple 1-H-pyrrole-3-carboxylic acid. 1-Tritylpyrrole-3-carboxylic acid has been converted efficiently into 3-aminopyrroles via Curtius rearrangement of the derived azide: 3-amino-1-tritylpyrrole appears to exist in solution exclusively as its imino-Δ4-pyrroline tautomer. 1-H-3-t-Butyloxycarbonylaminopyrrole udergoes trifluoroacetylation regioselectively at the 2-position.Metallation of 1-tritylpyrrole with butyl-lithium in hexamethylphosphoric triamide gives rise to the unexpected products 9-phenylfluorene, 1-methoxycarbonylpyrrole and methyl triphenylmethylacetate (after work-up of the lithio-intermediates with carbon dioxide and methylation of the resulting acids).
- Chadwick, Derek J.,Hodgson, Simon T.
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- PRIMARY AMINES VIA ELECTROPHILIC AMINATION OF ORGANOMETALLIC COMPOUNDS WITH O-(DIPHENYLPHOSPHINYL)HIDROXYLAMINE
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It is shown that O-(diphenylphosphinyl)hydroxylamine 4a transforms all kinds of "carbanions" into primary amines; best yields are received with "stabilized anions", e.g. of the benzylic type.
- Boche, Gernot,Bernheim, Michael,Schrott, Wolfgang
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p. 5399 - 5402
(2007/10/02)
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- On the Basicity of Triarylmethylamines in Solution
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The pKa* of 11 triarylmethylamines (tritylamines), eight of which are new, and some related bases were measured in methylcellosolve/water 80:20 (MCS); some were also measured in dioxane/water 60:40 (Dx), acetonitrile (An), nitrobenzene (Nb) and acetic acid (Ac). 1) The influence of the aryl groups on the basicity is essentially additive; 2) In different solvents, similar linear free energy relationships were found, with differences in ρ* characteristic of solvation; 3) The influence on basicity of substituents of the aryl groups follows Hammett's relationship.These results indicate a preponderance of inductive effects.N,N-Dimethyltritylamine (3b) pKaMCS = 3.40) shows a marked crowding effect, absent in the isomeric tertiary amines 13 and 14.Tri-p-nitrotritylamine (10a) 8pKaMCS = 3.10), N,N-dimethyl-tri-p-nitrotritylamine (10b) (pKaAc = 0.50), and 3b are particularly weak bases; the baseweakenning effect of the trinitrotrityl group is similar to that of the cyanomethyl and trifluoroethyl groups.
- Dahn, Hans,Farine, Jean-Claude,Nguyen, Thi Thanh Tam
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p. 780 - 787
(2007/10/02)
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