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Synthesis and biological properties of novel structural analogs of isothiobarbamine
Novel structural analogs of isothiobarbamine, which differ from the prototype scaffold by the substituent at position 2 of the pyrimidine heterocycle, were for the first time synthesized and characterized. Data acquired in pharmacological experiments in vivo revealed that compounds 1b—d and 10 increase physical productivity, whereas compounds 1c and 10 exhibit a nootropic effect, compound 8a shows a psychostimulating effect, and compound 1b exhibits anxiolytic properties. The results reported herein indicate that the drug discovery based on new structural analogs of isothiobarbamine is promising since it may lead to drugs for the prevention and treatment of asthenia (chronic fatigue syndrome).
Bakulin, D. A.,Brunilina, L. L.,Chapurkin, V. V.,Kovalev, N. S.,Kurkin, D. V.,Nawrozkij, M. B.,Novakov, I. A.,Ruchko, E. A.,Sablina, L. A.,Salykin, N. A.,Sheikin, D. S.,Tyurenkov, I. N.,Vernigora, A. A.,Vorontsov, M. Yu.,Vostrikova, O. V.
p. 2220 - 2226
(2022/01/22)

Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes
Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.
Zhang, Yang,Torker, Sebastian,Sigrist, Michel,Bregovi?, Nikola,Dydio, Pawe?
supporting information
p. 18251 - 18265
(2020/11/02)

Michaelis-Arbuzov-type reaction of 1-imidoalkyltriarylphosphonium salts with selected phosphorus nucleophiles
In this study, Michaelis-Arbuzov-type reaction of 1-imidoalkyltriarylphosphonium salts with phosphites, phosphonites, and phosphinites was used in the synthesis of a wide range of phosphorus analogs of α-amino acids such as 1-imidoalkylphosphonates, 1-imidoalkylphosphinates, and 1-imidoalkylphosphine oxides. Large differences were observed in the reactivity of substrates depending on their structure, especially on the type of phosphonium moiety and N-protecting group. The conditions under which the expected products can be obtained in good to excellent yields have been developed. Mechanistic aspects of the transformation have been provided.
Adamek, Jakub,egrzyk-Schlieter, Anna W.,Ste?, Klaudia,Walczak, Krzysztof,Erfurt, Karol
(2019/09/30)

Normal Alpha Olefin Synthesis Using Dehydroformylation or Dehydroxymethylation
The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, 1-decene, and 1-dodecene in a multistep synthesis scheme from another normal alpha olefin. Also disclosed are reactions for converting aldehydes, primary alcohols, and terminal vicinal diols into normal alpha olefins.
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Paragraph 0127; 0128; 0129

(2019/09/06)

Oxidative Dehydroxymethylation of Alcohols to Produce Olefins
Catalyst compositions for the conversion of aldehyde compounds and primary alcohol compounds to olefins are disclosed herein. Reactions include oxidative dehydroxymethylation processes and oxidative dehydroformylation methods, which are beneficially conducted in the presence of a sacrificial acceptor of H2 gas, such as N,N-dimethylacrylamide.
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Paragraph 0058

(2019/09/06)

Regio- and Stereoselective Chan-Lam-Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines
Efficient and scalable Cu(II)-mediated enol esterification methodology of carboxylic acids from alkenyl boroxines and boronic acids is presented. The reaction shows a wide scope in aliphatic and aromatic carboxylic acids in combination with several alkenyl boroxines. In the case of 2-substituted alkenyl boroxines the double bond configuration was fully retained in the enol ester product. Also N-hydroxyimides and imides could be transformed in the respective amidooxy vinyl enol ethers and vinyl enamides. Finally, with the exception of methionine, all other 19 canonical amino acids showed their compatibility to give the enol esters in a stereoselective fashion. (Figure presented.).
Steemers, Luuk,Wijsman, Linda,van Maarseveen, Jan H.
supporting information
p. 4241 - 4245
(2018/10/02)

Tandem Catalysis: Transforming Alcohols to Alkenes by Oxidative Dehydroxymethylation
We report a Rh-catalyst for accessing olefins from primary alcohols by a C-C bond cleavage that results in dehomologation. This functional group interconversion proceeds by an oxidation-dehydroformylation enabled by N,N-dimethylacrylamide as a sacrificial acceptor of hydrogen gas. Alcohols with diverse functionality and structure undergo oxidative dehydroxymethylation to access the corresponding olefins. Our catalyst protocol enables a two-step semisynthesis of (+)-yohimbenone and dehomologation of feedstock olefins.
Wu, Xuesong,Cruz, Faben A.,Lu, Alexander,Dong, Vy M.
supporting information
p. 10126 - 10130
(2018/08/23)

1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents
An effective synthesis of the hitherto unknown 1-imidoalkylphosphonium salts has been developed in the reported study. The crucial step in the method included the decarboxylative α-methoxylation of N-phthaloyl- or N-succinylamino acids to the corresponding N-(1-methoxyalkyl)imides, followed by the displacement of the methoxy group by the triarylphosphonium group through melting of the imide derivative with triarylphosphonium tetrafluoroborate. The imidoalkylating properties of the obtained 1-imidoalkylphosphonium salts were tested using the Tscherniac–Einhorn-type reaction with aromatic hydrocarbons as a model reaction. It was found that the Cα–P+ bond strength can be considerably reduced and the imidoalkylation of arenes can be markedly facilitated using 1-imidoalkylphosphonium salts derived from triarylphosphines with electron-withdrawing substituents such as tris(m-chorophenyl)phosphine, tris(p-chlorophenyl)phosphine and tris[p-(trifluoromethyl)phenyl]phosphine. Microwave irradiation also considerably facilitates the cleavage of the highly polar Cα–P+ bond.
Adamek, Jakub,Mazurkiewicz, Roman,W?grzyk, Anna,Erfurt, Karol
p. 1446 - 1455
(2017/08/02)

Application of Pd Nanoparticles Supported on Mesoporous Hollow Silica Nanospheres for the Efficient and Selective Semihydrogenation of Alkynes
Herein, the preparation of a heterogeneous catalyst consisting of 1-2 nm sized Pd nanoparticles supported on amino-functionalized mesoporous hollow silica nanospheres and its use for the semihydrogenation of mono- And disubstituted alkynes is reported. By utilizing this Pd nanocatalyst together with the green poisoning agent DMSO, high yields of the desired alkenes could be achieved, while suppressing the degree of over-reduction to alkanes. To our delight, the Pd nanocatalyst displayed remarkable chemoselectivity towards the alkyne moiety, allowing the transformation to be carried out in the presence of other reducible functionalities, such as halogens, carbonyl, and nitro groups.
Verho, Oscar,Zheng, Haoquan,Gustafson, Karl P. J.,Nagendiran, Anuja,Zou, Xiaodong,B?ckvall, Jan-E.
p. 773 - 778
(2016/03/05)

Metal-free C-N cross-coupling of electrophilic compounds and N-haloimides
When DBU is added, the cross-coupling reaction between alkyl halides (halogen = Cl, Br and I) and N-haloimides (halogen = Cl, Br) occurs, resulting in the formation of aminated products. A halogen bond activated nucleophilic substitution mechanism was proposed. The methodology represents an elegant example of applying the halogen bond activation strategy in an organic transformation.
Zhang, Luyan,Li, Yanru,Jin, Long-Yi,Liang, Fushun
p. 65600 - 65603
(2015/08/18)

Chiral Pool-Based Synthesis of Naphtho-Fused Isocoumarins
A variety of chiral derivatives of benzo[d]naphtho[1,2-b]pyran-6-one were prepared in a single step by Et3N-mediated condensation of homophthalic anhydride with different derivatives of (S)-amino acid chlorides at -5 °C by employing a chiral pool methodology. Chirality 27:951-957, 2015.
Raza, Abdul Rauf,Saddiqa, Aisha,?akmak, Osman
p. 951 - 957
(2015/11/16)

Chiron based synthesis of isocoumarins: Reactivity of α-substituted carboxylic acids
The asymmetric synthesis of a novel (S)-isocoumarin has been attempted in a single step by the coupling of homophthalic acid with (S)-N-protected amino acids and α-chloroacids at high temperature by exploiting a chiral pool methodology. The coupling of homophthalic acid with N-protected (S)-amino acids gave exclusion of the carboxyl/alkyl group. However, coupling of homophthalic acid with α-chloroacids afforded asymmetric isocoumarins in high yield.
Saddiqa, Aisha,Raza, Abdul R.,Black, David Stc.,Kumar, Naresh
p. 736 - 743
(2014/06/09)

Exploration of photochemical reactions of N-trimethylsilylmethyl- substituted uracil, pyridone, and pyrrolidone derivatives
Photochemical reactions of N-trimethylsilylmethyl-substituted uracil, pyridone and pyrrolidone derivatives were carried out to determine if silicone containing substituents have an impact on excited state reaction profiles. The results show that ultraviolet irradiation of N-trimethylsilylmethyl substituted uracils in the presence of substituted alkenes leads to efficient formation of both dimeric and cross [2+2]-cycloaddition products. Qualitatively similar observations were made in a study of the photochemistry of N- trimethylsilylmethyl-2-pyridone. The combined results demonstrate that [2+2]-photocycloaddition is a more efficient excited state reaction pathway for the uracil and pyridone substrates as compared to other processes, such as ylide-forming trimethylsilyl group C-to-O migration. Finally, photoreactions of N-trimethylsilylmethyl-2-pyrrolidone in solutions containing dipolarophiles, such as methyl acrylate, lead to the formation of the desilylation product, N-methyl-2-pyrrolidone by way of a simple, non-ylide generating, protodesilylation process. In addition, observations were made which show that orbital symmetry allowed photocycloreversion reactions of dimeric uracil derivatives, involving cyclobutane ring splitting, to take place. These processes, which lead to the formation of monomeric uracils, appear to be stimulated by the presence of electron donor groups on the cyclobutane ring, a likely result of a new SET promoted cyclobutane ring cleavage pathway. In the cases of N-trimethylsilylmethyl-substituted cyclobutane derivatives that possess phthalimide groups, highly efficient excited state cleavage of the cyclobutane moiety occurs to produce uracil derivatives and corresponding vinyl phthalimide. The Royal Society of Chemistry and Owner Societies 2011.
Cho, Dae Won,Lee, Chan Woo,Park, Jong Gu,Oh, Sun Wha,Sung, Nam Kyoung,Park, Hea Jung,Kim, Kyung Mok,Mariano, Patrick S.,Yoon, Ung Chan
experimental part
p. 1169 - 1180
(2012/06/01)

Direct N- and C-vinylation with trimethoxyvinylsilane
Treatment of nucleobases, nucleosides, 5-membered N-heterocycles and terminal alkynes with trimethoxyvinylsilane in the presence of copper(II) acetate-TBAF system as catalyst affords the vinylation products.
Arsenyan, Pavel,Petrenko, Alla,Paegle, Edgars,Belyakov, Sergey
experimental part
p. 326 - 328
(2012/02/04)

PROCESS FOR ALKENYLATING CARBOXAMIDES
The present invention relates to a process for preparing N-(1-alkenyl)carboxamides of the formula I, which comprises reacting a carboxamide of the formula II with an alkyne of the formula III in the presence of a catalyst selected from among carbonyl complexes, halides and oxides of rhenium, manganese, tungsten, molybdenum, chromium and iron.
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Page/Page column 8

(2009/05/28)

Synthesis of P,N-heterocycles from ω-amino-H-phosphinates: Conformationally restricted α-amino acid analogs
(Chemical Equation Presented) P,N-Heterocycles (3-hydroxy-1,3- azaphospholane and 3-hydroxy-1,3-azaphosphorinane-3-oxide) are synthesized in moderate yield from readily available ω-amino-H-phosphinates and aldehydes or ketones via an intramolecular Kabachnik-Fields reaction. The products are conformationally restricted phosphinic analogs of α-amino acids. The multigram-scale syntheses of the H2N(CH2) nPO2H2 phosphinic precursors (n = 1, 2, 3) and some derivatives are also described.
Queffelec, Clemence,Ribiere, Patrice,Montchamp, Jean-Luc
supporting information; experimental part
p. 8987 - 8991
(2009/04/11)

1,3-Dipolar cycloaddition of N-substituted dipolarophiles and nitrones: Highly efficient solvent-free reaction
(Chemical Equation Presented) New isoxazolidines were synthesized in good to excellent yields by 1,3-dipolar cycloaddition of N-vinylamide dipolarophiles and nitrones. Strikingly, solvent-free conditions gave high conversion and yields, shortened reaction time, and minimized degradation products. N-Vinyloxazolidin-2-one and its analogues used in these cycloaddition reactions were conveniently prepared in excellent yields by a modified version of Buchwald's one-step copper-catalyzed vinylation using vinyl bromide. From the adducts, a two-step access to various unsymmetric aspartate derivatives was also described.
Thanh, Binh Nguyen,Martel, Arnaud,Dhal, Robert,Dujardin, Gilles
p. 2621 - 2632
(2008/09/19)

The synthesis of some chiral 2-aminoalkyloxazole-4-carboxylates from isoxazol-5(2H)-ones
Ethyl 4-methyl-5-oxo-2,5-dihydroisoxazole-3-carboxylate can be N-acylated by a number of natural and synthetic phthalimidylamino acids in the presence of carbodiimides. The N-acyiated products form the corresponding oxazoles smoothly when irradiated at 300 nm in acetone. Removal of the phthalimido protecting group then gives 2-aminoalkyloxazole-4-carboxylate esters in good overall yields, and without significant racemization at any step.
Cox, Matthew,Prager, Rolf H.,Svensson, Carina E.
p. 887 - 896
(2007/10/03)

Process for preparing fluorine-containing phenethylamines and novel fluorine-containing β-iminovinyl-and β-iminoethylbenzenes
The present invention relates to a process for preparing fluorine-containing phenethylamines which is characterized in that, in a first step, a substituted bromobenzene is reacted with an N-vinylimide in the presence of a palladium catalyst, in a second step, the resulting substituted β-iminovinylbenzene is hydrogenated catalytically and in a third step, the substituted β-iminovinylbenzene obtained in the second step is cleaved. This process also provides access to novel β-iminovinyl- and β-iminoethylbenzenes.
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(2008/06/13)

The cohalogenation of 1-N-vinylpyrimidinediones: A new approach to nucleoside analogs
A new approach to the synthesis of nucleoside analogs has been developed, which involves initial chemo- and regioselective cohalogenation of 1-N-vinylpyrimidinediones 10a,b using N-bromosuccinimide in the presence of variously substituted propargylic alcohols. Radical carbocyclization of the resulting β-bromo propargylic ethers 17-22 then leads to 3- methylenetetrahydrofurans 23-26. In such cyclizations, different reactivities have been observed for diastereomers 22a,b obtained by cohalogenation with (R)-1-benzyloxybut-3-yn-2-ol; although the expected anti 3- methylenetetrahydrofurans 27a,b were obtained, the syn diastereomers 28a,b were only the minor constituents of a mixture in which bicyclonucleosides 29a,b were the major components. The formation of 29a,b results from a 1,6- hydrogen transfer followed by cyclization, which might be favored by a CH-π interaction in radical intermediate syn II.
Baret, Nathalie,Dulcere, Jean-Pierre,Rodriguez, Jean,Pons, Jean-Marc,Faure, Robert
p. 1507 - 1516
(2007/10/03)

Exploratory studies probing the intermediacy of azomethine ylides in the photochemistry of N-phthaloyl derivatives of α-amino acids and β-amino alcohols
Exploratory photochemical studies with N-phthaloyl derivatives of glutamic acid, aspartic acid, serine, threonine and analogous carboxylic acids and alcohols have been conducted to determine the generality of azomethine ylide forming decarboxylation and retro-aldol fragmentation reactions. Preferences in the competition between these excited state reaction pathways have been determined by studies with phthalimides which contain both α-amino acid and β-aminoethanol groups.
Yoon, Ung Chan,Lee, Chan Woo,Oh, Sun Wha,Mariano, Patrick S.
p. 11997 - 12008
(2007/10/03)

Photochemistry of Phthaloylcsteine, its methyl ester and C-unprotected S-Alkyl derivatives
N-Phthaloyl cysteine derivatives 1a-d were photochemically transformed by elimination, decarboxylation, and via electron transfer cyclization to the products 2,3,4 and 6-8. The spin selectivities of the singlet and triplet pathways were investigated in acetonitrile and acetone . The excited singlets were prone to elimination and γ-H abstraction (e.g. formation of 5) whereas the triplets cyclized to thiazinoisoindoles. This behavior can be correlated with efficiencies of forward and return electron transfer stepsversus homolytic hydrogen abstraction as exemplified for the cysteine substrate.
Griesbeck, Axel G.,Hirt, Joachim,Kramer, Wolfgang,Dallakian, Paul
p. 3169 - 3180
(2007/10/03)

Photochemical transformations of proteinogenic and non-proteinogenic amino acids
The photochemistry of N-activated enantiomerically pure α-amino acids is described with emphasis on chemo-, regio-, stereo-, and spin selectivity. An especially valuable chromophore is the phthalimido group. The first excited singlet states are short-lived and deactivated (chemically) via homolytic CH cleavage or (physically) via electron-transfer steps. The first excited triplet states are chemically deactivated via electron-transfer reactions and subsequent deprotonation/coupling steps. A wide variety of product types were synthesized, and potential target molecules were available by tuning the reaction conditions. Also remote groups can be activated by means of electron-transfer steps, which represents an attractive new synthetic protocol for macrocyclization.
Griesbeck, Axel G.
p. 272 - 283
(2007/10/03)

P(CH3NCH2CH2)3N: A Nonionic Superbase for Efficient Dehydrohalogenation
The commercially available nonionic Superbase P(CH3NH2CH2)3N (1) is far superior to DBU for the conversion of primary and secondary alkyl halides to alkenes. A reason for the efficacy of acetonitrile as a solvent for the halides requiring extended reaction times is presented.
Arumugam, Subramaniam,Verkade, John G.
p. 4827 - 4828
(2007/10/03)

Potential GABAB Receptor Antagonists. X* the Synthesis of Further Analogues of Baclofen, Phaclbfen and Saclofen
In an attempt to obtain new compounds with binding activity at the GABAB receptor site, we report the synthesis of 3-amino-2-arylpropanoic acids, and the sulfonic, phosphonic and hydroxamic acid analogues. In addition, we report the synthesis of the isomer of phaclofen, 3-amino-1-(4-chlorophenyl)-propylphosphonic acid, and the higher homologue of baclofen, 5-amino-2-(4-chlorophenyl)pentanoic acid.
Prager, Rolf H.,Schafer, Karl
p. 813 - 823
(2007/10/03)

Photochemistry of N-phthaloyl derivatives of electron-donor-substituted amino acids
The hydroxy substituted amino acids threonine and serine have been investigated concerning their photochemical behaviour when activated as N-phthaloyl substrates. The methyl esters 1a and 2a solely underwent cleavage of the central C-C single bond to give the glycine derivative 3 and an aldehyde fragment. C-unprotected threonine derivative 1b is converted into a series of products the composition of which depends on solvent polarity and on the electronic state. Three reaction modes were detected for the N-phthaloyl derivatives of the aryl substituted amino acids phenylalanine, tyrosine, and dihydroxyphenylalanine (DOPA): (A) decarboxylation (only for 12a), (B) β-fragmentation, and (C) ring enlargement reaction. Processes B and C are initiated by photo electron transfer (PET), as the solvent dependence revealed. The DOPA derivatives 14a and 14b are the most prominent examples due to their exclusive PET reactivity leading to type C products (18a,b) with high diastereoselectivity (90:10). PET results from the first excited singlet states of 12 and 13, whereas for compounds 14 the corresponding triplet states are involved. The correlation between photochemical reactivity and the fluorescence decay data for compounds 12a,b and 15 is discussed.
Griesbeck,Henz,Hirt,Ptatschek,Engel,Loffler,Schneider
p. 701 - 714
(2007/10/02)

ENHANCEMENT OF THE DIRECT 13C-1H COUPLING CONSTANT UPON PHYSICAL APPROXIMATION OF THE PROTON AND HETEROATOM IN N-VINYLHETEROCYCLES
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Afonin, A. V.,Vashchenko, A. V.,Danovich, D. K.,Trzhtsinskaya, B. V.,Baikalova, L. V.,Apakina, E. V.
p. 1538 - 1541
(2007/10/02)

A Novel, Base-induced Fragmentation of Hantzsch-type 4-Aryl-1,4-dihydropyridines
Hantzsch-type 1,4-dihydropyridine derivatives substituted with highly electron-deficient aryl groups in the 4-position, on treatment with a variety of basic reagents in non-hydroxylic solvents, undergo an unexpected and ready scission of the inter-ring bond to give the corresponding 4-unsubstituted pyridine and an arene derived from the original 4-substituent.The scope of the reaction has been investigated and possible mechanisms are discussed.
McInally, Thomas,Tinker, Alan C.
p. 1837 - 1844
(2007/10/02)

Organic Gas-Solid Reactions: Additions of HX to N-Vinylphthalimide and Substitutions of its Hydrate
Gas-solid additions of N-vinylphthalimide (1) and gas-solid substitutions of its isolable hydrate 5 with the dipolar gases HCl, HBr, HI yield quantitatively and surprisingly rapidly the reactive halogeno compounds 2, 3, 4, respectively.Their hydrolysis, depending on the conditions (gas: static, flow; liquid), gives 5 and the ether 7, alcoholysis and acetolysis the alkoxy(acetoxy) derivatives 8.Also gaseous bromine and (catalytically) water is added to crystalline 1.The mechanism of the rearrangement of N-(2-bromoethyl)- into N-(1-bromoethyl)phthalimide is established as a sequence of HBr-elimination and -addition.
Kaupp, Gerd,Matthies, Doris
p. 2387 - 2392
(2007/10/02)

Process for preparing cyclic N-vinylacylamines
Cyclic N-vinylacylamines are prepared by heating carbonic acid esters of cyclic N-2-hydroxyethylacylamines in the presence of a catalytic amount of alkali or alkaline earth metal compound having an alkaline reaction and subsequently distilling the reaction mixture. Cyclic N-vinylacylamines are valuable precursors for preparing plant protection agents and medicaments and serve as polymerization and copolymerization components for preparing plastics, surface coatings, paints and ion exchange materials.
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(2008/06/13)

AN UNUSUAL AMINAL DERIVATIVE FROM A MISDIRECTED GABRIEL SYNTHESIS
N-(2-bromoethyl)phthalimide (1) was reacted with sodium imidazolate in DMF to give the novel aminal N-phthalimide (4a) as well as N-vinylphthalimide (3) and the desired Gabriel intermediate 2.Aminal 4a as well as heterologues 4b - d form directly from rection of 3 with the appropriate heterocyclic sodium salt.
Press, J. B.,Haug, M. F.,Wright, W. B.
p. 837 - 842
(2007/10/02)

Photodecarboxylation of N-Phthaloyl-α-amino Acids
N-Phthaloylglycine (1a) was irradiated with a high pressure mercury lamp to give N-methylphthalimide (2a) in an excellent yield.N-Phthaloyl derivatives 1b-k of other α-amino acids also afforded the decarboxylated products 2b-k.In the cases of N-phthaloylserine (11) and di-phthloylcystine (1m), N-vinylphthalimide (3) was isolated as a major product.On the other hand, N-phthaloylmethionine (11a) and methyl N-phthaloylmethionate (11b) were treated in the same manner to give the aza-thiacyclo-heptanol derivatives 12a-b having a new ring system.Solvent effects and possible pathways of these reactions were examined.Keywords- N-phthaloyl-α-amino acid; photolysis; decarboxylation; cyclization; efficiency; solvent effect; υ-hydrogen abstraction
Sato, Yasuhiko,Nakai, Hideo,Mizoguchi, Tomishige,Kawanishi, Masazumi,Hatanaka, Yasumaru,Kanaoka, Yuichi
p. 1263 - 1270
(2007/10/02)

Palladium-Catalyzed Vinylic Substitution Reactions. An Approach to (Aminoalkyl)phencyclidines
4-Iodophencyclidine (5) was reacted with various N-alkenylphthalimides in the presence of 1 mol percent palladium acetate, triethylamine, and tri-o-tolylphosphine in acetonitrile as solvent at 100 deg C to give good yields of (E)-4-(phthalimidoalkenyl)phencyclidines (9a-c).Catalytic hydrogenation of the olefins gave 12a-c, and cleavage of the phthalimido moiety gave the desired 4-(aminoalkyl)phencyclidines (2a-c) which were characterized as their mixed thioureas.Amine 2b was also synthesized by reduction of the palladium-catalyzed phencyclidine-acrylonitrile adduct.Reaction of acrolein ethylene ketal with 5 in the presence of palladium acetate did not give adduct 15 but rather gave isomerized ketene acetal 17 which underwent further reaction to 16a or hydrolyzed to 16b upon workup.Transesterification of 16 with methanol gave methyl ester 18 which was identical with the ester obtained by catalytic reduction of the palladium-catalyzed adduct of 5 and methyl acrylate, 19.LAH reduction of 19 gave a 4/1 mixture of alcohols 21 and 22.Mass spectra and 13C NMR spectra are presented for these phencyclidines.
Johnson, Peter Y.,Wen, Jing Quan
p. 2767 - 2771
(2007/10/02)