- An efficient, stereocontrolled and versatile synthetic route to bicyclic partially saturated privileged scaffolds
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Herein, we describe the development of a simple, high yielding and stereocontrolled strategy for the synthesis of a series of triazolopiperazines and other biologically relevant fused scaffolds from optically active amino acids. This route was applied to the synthesis of 22 scaffolds containing new, previously inaccessible vectors and used to access a novel analogue of ganaplacide.
- Bond, Andrew D.,Hanby, Abigail R.,King, Thomas A.,Moss, Thomas A.,Sore, Hannah F.,Spring, David R.,Stewart, Hannah L.
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supporting information
p. 6818 - 6821
(2020/07/04)
-
- Efficient synthesis of methyl (S)-4-(1-methylpyrrolidin-2-YL)-3-oxobutanoate as the key intermediate for tropane alkaloid biosynthesis with optically acitve form
-
Methyl (S)-4-(1-methylpyrrolidin-2-yl)-3-oxobutanoate has been synthesized for enzymatic studies on cyclization enzymes during cocaine biosynthesis in Erythroxylum coca plants. During the present new synthesis, L-proline was first protected with Cbz group and reduced to chiral amino alcohol, which were then followed by Swern oxidation, Wittig reaction and decarboxylative condensation. At the last step, N-methylamino acid precursor was treated with 1,1'-carbonyldiimidazole followed by reacting with methyl potassium malonate to give the 3-oxobutanoate in 54% overall yield. This new strategy has proven to avoid obvious racemization of the L-proline chiral center during the synthesis. In addition, six of the eight synthesis steps were performed via GAP chemistry/technology without the use of column chromatography for purification.
- Katakam, Nanda Kumar,Seifert, Cole W.,D'Auria, John,Li, Guigen
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p. 604 - 613
(2019/08/01)
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- IDO INHIBITORS
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There are disclosed compounds that modulate or inhibit the enzymatic activity of indoleamine 2,3-dioxygenase (IDO), pharmaceutical compositions containing said compounds and methods of treating proliferative disorders, such as cancer, viral infections and/or inflammatory disorders utilizing the compounds of the invention.
- -
-
Paragraph 1621
(2016/10/27)
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- Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess
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The noncovalent combination of a supramolecular host with iminium organocatalysis is described. Due to cation–π interactions the reactive iminium species is held inside the host and reacts in this confined environment. The products formed differ up to 92 % ee from the control experiments without added host. A model rationalizing the observed difference is presented.
- Br?uer, Thomas M.,Zhang, Qi,Tiefenbacher, Konrad
-
supporting information
p. 7698 - 7701
(2016/07/07)
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- A lanthanide(III) triflate mediated macrolactonization/solid-phase synthesis approach for depsipeptide synthesis
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The effect of dysprosium(III) triflate on macrolactonization reactions to form depsipeptides using MNBA (Shiina's reagent) is reported. Improved yields were obtained for the formation of 16-membered depsipeptides using lanthanide triflate additives. The use of a macrocyclization strategy permits the use of a semiautomated solid-phase synthesis approach for the rapid synthesis of analogues of the antibacterial A54556 acyldepsipeptides in only two physical operations, requiring only final product purification after cyclization.
- Goodreid, Jordan D.,Dos Santos Da Silveira, Eduardo,Batey, Robert A.
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supporting information
p. 2182 - 2185
(2015/05/13)
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- Stereodivergent total synthesis of chlorofusin and its all seven chromophore diastereomers
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Chlorofusin (1), one of few natural antagonists against p53-MDM2 interactions, is a naturally biogenetic hybrid composed of a 27-membered nonacyclopeptide and a unique chromophore through the hydrocarbon linkage with ornithine. In this article, we describ
- Qiu, Hai-Bo,Qian, Wen-Jian,Yu, Shun-Ming,Yao, Zhu-Jun
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p. 370 - 380
(2015/02/19)
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- BIARYL INHIBITORS OF THE SODIUM CHANNEL
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The invention relates to compounds useful in treating conditions associated with voltage- gated ion channel function, particularly conditions associated with sodium channel activity. More specifically, the invention concerns biaryl derivatives (e.g., compounds according to any of Formulas (I)-(XII) or Compounds (l)-(372) of Table 1) that are that are useful in treatment of conditions such as epilepsy, cancer, pain, migraine, Parkinson's Disease, mood disorders, schizophrenia, psychosis, tinnitus, amyotropic lateral sclerosis, glaucoma, ischaemia, spasticity disorders, obsessive compulsive disorder, restless leg syndrome and Tourette syndrome.
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Page/Page column 43
(2013/09/12)
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- Practical one-pot double functionalizations of proline
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Solubilization of proline as the triethylammonium salt allows N-protection (as the Boc, Cbz or Moc derivative) and subsequent esterification or amidation of the carboxy terminus to be performed in an efficient one-pot fashion. Based on this concept, highly practical protocols were developed to prepare a series of proline derivatives (including Pro-Ser dipetides, Weinreb amides and N-protected proline esters), which are important intermediates, for instance, for the synthesis of proline-derived peptides, chiral reagents and catalysts for asymmetric synthesis. Georg Thieme Verlag Stuttgart - New York.
- Huy, Peter,Schmalz, Hans-Guenther
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experimental part
p. 954 - 960
(2011/05/07)
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- An efficient synthesis of sulfamides
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Here we report an efficient synthesis of sulfamides. 3,5-Lutidine was found to be an optimal solvent and catalyst for the reaction. The method was developed during our efforts to synthesize a series of novel FKBP-12 inhibitors in which the known ketoamide linker was replaced with sulfamide.
- Guo, Chuangxing,Dong, Liming,Kephart, Susan,Hou, Xinjun
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scheme or table
p. 2909 - 2913
(2010/06/14)
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- Oxoammonium salt/NaClO2: An expedient, catalytic system for one-pot oxidation of primary alcohols to carboxylic acids with broad substrate applicability
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A facile, green, one-pot oxidation of primary alcohols to carboxylic acids with broad substrate applicability has been developed by employing an expedient catalytic system consisting of 1-Me-AZADO+X-/NaClO 2. The Royal Society of Chemistry.
- Shibuya, Masatoshi,Sato, Takahisa,Tomizawa, Masaki,Iwabuchi, Yoshiharu
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supporting information; experimental part
p. 1739 - 1741
(2009/08/08)
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- PROCESS FOR PRODUCING CARBOXYLIC ACID FROM PRIMARY ALCOHOL
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To provide an industrially-useful and environmentally-friendly novel oxidation reaction. A process for producing a carboxylic acid from a primary alcohol, which comprises using an alkali metal chlorite as a co-oxidizing agent and using, as a catalyst, an oxoammonium salt of the formula (1):
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Page/Page column 5-7
(2009/05/28)
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- Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively
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We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.
- Nakatsuji, Hidefumi,Morimoto, Mami,Misaki, Tomonori,Tanabe, Yoo
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p. 12071 - 12080
(2008/03/13)
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- Large nonlinear effect observed in the enantiomeric excess of proline in solution and that in the solid state
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(Chemical Equation Presented) A clue to the origin of chirality? A solution of proline with high enantiomeric excess (85-99% ee) was obtained from solid proline of only 10% ee through novel dissolution and crystallization processes (see scheme). This observation may be an explanation for the origin of chirality on Earth.
- Hayashi, Yujiro,Matsuzawa, Masayoshi,Yamaguchi, Junichiro,Yonehara, Sayaka,Matsumoto, Yasunobu,Shoji, Mitsuru,Hashizume, Daisuke,Koshino, Hiroyuki
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p. 4593 - 4597
(2007/10/03)
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- Enzyme-catalyzed enantiomeric resolution of N-Boc-proline as the key-step in an expeditious route towards RAMP
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For the preparation of both enantiomers of N-carbamoyl-2-methoxymethylpyrrolidine, the precursors of Enders' chiral auxiliaries, SAMP and RAMP, enzyme-catalyzed kinetic resolution of racemic N-carbamoyl, N-Boc, N-Cbz proline esters and prolinols were examined. B. licheniformis protease (subtilisin) preferentially hydrolyzed the (R)-carbamoylproline ester with an enantiomeric ratio (E) of 10. To a hydrophobic N-Cbz proline ester, subtilisin showed lower selectivity (E=2.8), and in contrast, a purified protease (isozyme A) from the earthworm showed the preference of (S)-enantiomer (E=13.6). In a practical sense, C. antarctica lipase B (Chirazyme L-2) was effective for the hydrolysis of both N-Boc and N-Cbz derivatives with E >100. The e.e. of (R)-N-carbamoyl-2-methoxymethylpyrrolidine was raised to be >99.9% by recrystallization at the N-Boc-prolinol stage, which was derived from the (R)-N-Boc-proline methyl ester (98.7% e.e.) through a preparative-scale enzyme-catalyzed resolution (49% yield) of the racemic substrate.
- Kurokawa, Masayuki,Shindo, Takeyuki,Suzuki, Masumi,Nakajima, Nobuyoshi,Ishihara, Kohji,Sugai, Takeshi
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p. 1323 - 1333
(2007/10/03)
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- Simple, Mild, and Practical Esterification, Thioesterification, and Amide Formation Utilizing p-Toluenesulfonyl Chloride and N-Methylimidazole
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We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p-toluenesulfonyl chloride (TsCl) together with N-methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N-methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N-Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β-methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful 1H NMR monitoring study.
- Wakasugi, Kazunori,Iida, Akira,Misaki, Tomonori,Nishii, Yoshinori,Tanabe, Yoo
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p. 1209 - 1214
(2007/10/03)
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- A new pathway to chiral tetracyclic indolidines via Pauson-Khand reaction
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Reaction of enynes 1 and 3 with Co2(CO)8 in the presence of DMSO, NMO or TMANO as promoters produced tricyclic indolidine derivatives 5 and 7 stereoselectively in moderate to excellent yield. The stereochemistry at the C-7 position of the indolidines 5 and 7 was confirmed by their conversion into the bridged azacycles 10 and 13.
- Tanimori, Shinji,Fukubayashi, Kouji,Kirihata, Mitsunori
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p. 4013 - 4016
(2007/10/03)
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- A novel approach to the enantioselective formal synthesis of pumiliotoxin 251D
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An efficient enantioselective synthesis of the indolizidine framework 9 of pumiliotoxin 251D in good yield by using a Lewis acid (cat.)-promoted diastereoselective addition of ethyl lithiopropiolate to ketone 7 derived from L-proline as a key step is reported. Hydrogenation of the addition product 8a gave the desired lactam 9. At the same time the 8-epimer of 9 was synthesized for the first time.
- Ni, Yike,Zhao, Gang,Ding, Yu
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p. 3264 - 3266
(2007/10/03)
-
- Unexpected diastereoselectivity in AD of an L-proline-derived 1,1- disubstituted alkene
-
Asymmetric dihydroxylation of the L-proline-derived 1,1-disubstituted alkene 5 catalysed by either (DHQ)2PHAL or (DHQD)2PHAL unexpectedly leads to preference for the same diastereomer 7, both reactions proceeding with apparently matching double diastereoselectivity. In contrast, AD using the analogous (DHQ)2PYR or (DHQD)2PYR ligands leads to preferences for diols 7 or 8 respectively.
- Gardiner, John M.,Bruce, Sarah E.
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p. 1029 - 1032
(2007/10/03)
-
- 111. Synthesis of a novel tricyclic dipeptide template and its incorporation into a cyclic peptide mimetic containing an NPNA motif
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A novel tricyclic dipeptide template, formally derived by coupling (2S,4S)-4-aminoproline (Pro(NH2)) and (S)-2-(carhoxymethyl)proline (Pro(CH2COOH)) as a diketopiperazine, has been synthesized in a form suitable for solid-phase peptide synthesis using Fmoc chemistry. This template was incorporated into the cyclic molecule cyclo(-Ala1-Asn2-Pro3- Asn4-Ala5-Ala6-Temp-) (Temp = template), whose conformation in H2O was studied by NMR methods. Average solution structures derived by restrained simulated annealing point to a highly populated βI-turn within the Asn-Pro- Asn-Ala motif and also indicate which conformations are likely to be preferred by the template.
- Pfeifer, Marc E.,Linden, Anthony,Robinson, John A.
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p. 1513 - 1527
(2007/10/03)
-
- Synthesis of [6-13C]-L-lysine
-
A short and efficient enantioselective synthesis of [6-13C]-L-lysine from commercially available N-benzyloxycarbonyl-L-glutamic acid α-methyl ester is described using [13C]-sodium syanide as the source of isotopic label.
- Sutherland,Willis
-
-
- Facile new method for preparation of optically active protected proline
-
Treatment of L-N-protected 2-amino-5-bromopentanoic acid ester, which was prepared from protected L-glutamic acid, with sodium hydride in tetrahydrofuran (THF) proceeded to give the corresponding protected L-proline in high yield. On the other hand, the reaction of 2-aminobutyric acid derivative with sodium hydride gave the 1-aminocyclopropane-1-carboxylic acid derivative.
- Yamaguchi, Jun-Ichi,Ueki, Masaaki
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p. 621 - 622
(2007/10/03)
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- A short and highly stereocontrolled total synthesis of (3R,5R,8aR)-3-n-Butyl-5-methylindolizidine
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Total synthesis of (-) (3R,5R,8aR)-3-n-Butyl-5-methylindolizidine is described in 9 steps (22% overall yield) from L-proline.
- Celimene, Catherine,Dhimane, Hamid,Le Bail, Marc,Lhommet, Gerard
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p. 6105 - 6106
(2007/10/02)
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- Dicarbonates: Convenient 4-dimethylaminopyridine catalyzed esterification reagents
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The DMAP (4-dimethylaminopyridine) catalyzed reaction of dialkyl dicarbonates la-e and carboxylic acids 2 afforded the corresponding esters 5 in good yield.
- Takeda,Akiyama,Nakamura,Takizawa,Mizuno,Takayanagi,Harigaya
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p. 1063 - 1066
(2007/10/02)
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- DERIVATIVES OF HETEROCYCLIC α-IMINOCARBOXYLIC ACIDS. 3. SYNTHESIS OF N-ALKOXYCARBONYL AND N-ALKOXYCARBONYLALKENYL DERIVATIVES OF α-IMINOCARBOXYLIC ACIDS.
-
By the interaction of L-proline, L-thioproline, pipecolic acid, tetrahydro-1,4-thiazine-3-carboxylic acid, and diastereomeric esters of tetrahydro-1,4-thiazine-3,5-dicarboxylic acid with methyl chloroformate, methyl propiolate, and acetylenecarboxylic aci
- Nurdinov, R.,Liepin'sh, E. E.,Kalvin'sh, I. Ya.
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p. 1347 - 1351
(2007/10/02)
-
- DERIVATIVES OF HETEROCYCLIC α-IMINOCARBOXYLIC ACIDS. 4. REDUCTION OF N-ALKOXYCARBONYL DERIVATIVES OF α-IMINOCARBOXYLIC ACIDS.
-
When N-methoxycarbonyl and N-benzoxycarbonyl derivatives of methyl esters of aziridine-2-carboxylic acid, L-proline, L-thioproline, and pipecolic acid interact with NaBH4 in tert-butanol/methanol, the products of reduction of the C-methoxycarbonyl group o
- Nurdinov, R.,Liepin'sh, E. E.,Kalvin'sh, I. Ya.
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p. 1352 - 1357
(2007/10/02)
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- Syntheses and Reactions of Silyl Carbamates. 1. Chemoselective Transformation of Amino Protecting Groups via tert-Butyldimethylsilyl Carbamates
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The N-tert-butyldimethylsilyloxycarbonyl group (silyl carbamate) was synthesized from commonly used amino protecting groups such as N-tert-butoxycarbonyl (Boc) and N-benzyloxycarbonyl (Z) by treatment with tert-butyldimethylsilyl trifluoromethanesulfonate/2,6-lutidine and tert-butyldimethylsilane/Pd(OAc)2, respectively.This novel species, upon activation with fluoride ion, reacts with a variety of electrophiles to give N-ester type compounds in high yield.For example, the conversion of N-t-Boc compounds into their corresponding N-Z compounds via a silyl carbamate was accomplished under these mild reaction conditions.
- Sakaitani, Masahiro,Ohfune, Yasufumi
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p. 870 - 876
(2007/10/02)
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- A highly enantioselective synthesis of phosphate triesters
-
A general methodology for the preparation of both enantiomers of a variety of trialkyl phosphates with enantiomeric excesses ranging from 87 to 92% is described. Bis(2,4-dichlorophenyl) phosphoramidates bearing a 2-substituted pyrrolidine moiety as the chiral auxiliary are prepared and examined for their stereoselectivity. Considerations based on both the absolute configuration of the product phosphates as well as the X-ray structural determination of one of the bis(2,4-dichlorophenyl) phosphoramidates suggest these substitutions occur with preponderant inversion of configuration at phosphorus.
- Nakayama, Kensaku,Thompson, Wayne J.
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p. 6936 - 6942
(2007/10/02)
-
- Enantioselective reduction of ketones
-
Chiral 1,3,2-oxazaborolidines and tetrahydro-1,3,2-oxazaborines are effective catalysts for the borane reduction of prochiral ketones to optically active alcohols.
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-
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- Process for the preparation of the (-)-antipode of (E)-1-cyclohexyl-4, 4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-yl)-pent-1-ene
-
A process for the preparation of the (-)-antipode of (E)-1-cyclohexyl-4,4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-yl)-pent-1-ene of the formula STR1 which comprises reacting the (E)-isomer of 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one of the formula STR2 (a) with boron hydride in the presence of an optically active proline derivative of the formula STR3 in which, R1 is alkyl, phenyl or benzyl, or (b) with a complex borohydride in the presence of an acid addition salt of the optically active proline derivative, in the presence of a diluent at a temperature between about -70° C. and +60° C. The proline derivatives are also new and are produced from S-proline esters. The end product is a known plant growth regulant.
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- Tertiary-butyldimethylsilyl carbamate derivative and process for producing the same
-
A t-butyldimethylsilyl carbamate derivative and a process for producing the same are disclosed. Tertiary-butyldimethylsilyl carbamate derivatives having the following general formula (1) are intermediates for the production of a variety of carbamate ester
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- Enantioselective Carbon-Carbon Bond Formation by Chiral Organotitanium Compounds; Methyltitanium (S)-N-Acylpyrrolidinyl-methoxide Diisopropoxides
-
New chiral compounds, (S)-N-acylpyrrolidinylmethanols (1b-f and 1h), were synthesized and chiral methyltitanium diisopropoxides (2a-h) were prepared from 1a-h.Enantioselective carbon-carbon bond formation between aromatic carbaldehydes and 2a-h was achieved in yields of 90-97 percent and 10.5-54.1 percent ee.The chiral auxiliaries (1a-h) were recovered in almost quantitative yields without any loss of optical purity.Keywords: (S)-N-acylpyrrolidinylmethanol; carbon-carbon bond formation; enantioselective reaction; methyltitanium diisopropoxide; (R)-1-(1-naphthyl)ethanol; (R)-1-phenylethanol; (S)-prolinol
- Takahashi, Hiroshi,Kawabata, Akihiro,Higashiyama, Kimio
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p. 1604 - 1607
(2007/10/02)
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- A versatile and efficient synthesis of carbinolamine-containing pyrrolo[1,4]benzodiazepines via the cyclization of N-(2-aminobenzoy 1)pyrrolidine-2-carboxaldehyde diethyl thioacetals: Total synthesis of prothracarcin
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A versatile and efficient synthesis of carbinolamine-containing pyrrolo[1,4]benzodiazepines (or the corresponding imine forms) of types 2, 7, and 8 is described that involves mercuric chloride mediated cyclization of the corresponding N-(2-aminobenzoyl)py
- Langley, David R.,Thurston, David E.
-
-
- A Novel Synthesis of L-Pyroglutamic Acid Derivatives from L-Proline: Utility of N-Protecting Groups for Ruthenium Tetroxide Oxidation of Cyclic α-Amino Acids
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The utility of four urethane type N-protecting groups, benzyloxycarbonyl (Z), p-nitrobenzyloxycarbonyl , trichloroethoxycarbonyl (Troc) and tert-butoxycarbonyl (Boc) groups, was tested in the ruthenium tetroxide (RuO4) oxidation of N-protected L-proline esters.Three groups, but not the Z group, which was decomposed by RuO4, were found to be stable during the oxidation and afforded high yields of the corresponding L-pyroglutamic acid esters.Removal of the protecting groups from the oxidation products was carried out successfully in the usual manner to give N-unsubstituted (NH-type) L-pyroglutamic acid derivatives without racemization.The first transformation of L-proline into L-pyroglutamic acid and its derivatives has been accomplished.Keywords - oxidation; ruthenium tetroxide oxidation; lactam synthesis; L-pyroglutamic acid synthesis; carboxamide N-protection; ruthenium tetroxide; L-proline; L-pyroglutamic acid; twophase method.
- Yoshifuji,Shigeyuki,Tanaka, Ken-ichi,Kawai, Tomoyuki,Nitta, Yoshihiro
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p. 3873 - 3878
(2007/10/02)
-
- SELECTIVE TRANSFORMATION OF N-t-BUTOXYCARBONYL GROUP INTO N-ALKOXYCARBONYL GROUP via N-CARBOXYLATE ION EQUIVALENT
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Reaction of a variety of N-t-butoxycarbonyl compounds with t-butyldimethylsilyl trifluoromethanesulfonate afforded the N-t-butyldimethylsilyloxycarbonyl compounds, chemoselectively, which upon treatment with an alkyl or aryl halide provided the corresponding N-alkoxy- or N-aryloxycarbonyl compounds, efficiently.
- Sakaitani, Masahiro,Ohfune, Yasufumi
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p. 5543 - 5546
(2007/10/02)
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- Syntheses of Substituted L- and D-Tryptophans
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Several 5-substituted nb-methoxycarbonyl-L- and -D-tryptophan derivatives were synthesized from proline by a new route involving electrochemical oxidation, as well as by the known procedures.Removal of the Nb-methoxycarbonyl group was accomplished by treatment with Me3SiI in refluxing chloroform, then alkaline hydrolysis of the methyl esters afforded 5-substituted L- and D-tryptophans with high optical purities.Keywords - L-tryptophan 5-substituted; D-tryptophan 5-substituted; anodic oxidation; N-methoxycarbonyl group deprotection; Fischer indole synthesis; iodotrimethylsilane
- Irie, Kunihiko,Ishida, Akihiko,Nakamura, Tohru,Oh-ishi, Tokuro
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p. 2126 - 2139
(2007/10/02)
-
