- Preparation method of (S)-3-hydroxypiperidine
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The invention discloses a preparation method of (S)-3-hydroxypiperidine. The preparation method comprises the steps of (1) carrying out catalytic hydrogenation on 3-hydroxypyridine to prepare 3-hydroxypiperidine; (2) splitting the 3-hydroxypiperidine for preparing the (S)-3-hydroxypiperidine, wherein catalytic hydrogenation is carried out under the co-catalysis of a ruthenium/silicon dioxide catalyst and a cocatalyst; the weight ratio of the ruthenium/silicon dioxide catalyst to the cocatalyst is 1:1 to 3:1; the total weight of the ruthenium/silicon dioxide catalyst and the cocatalyst is 5 to10 percent of the weight of the 3-hydroxypiperidine; and the cocatalyst is aluminum oxide. According to the method provided by the invention, the ruthenium/silicon dioxide catalyst and the aluminum oxide are adopted as a compound catalyst for catalytic hydrogenation, and the compound catalyst is relatively cheap but has the same better catalysis effect, and pollutes environment less so as to be suitable for industrial production.
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Paragraph 0028
(2018/06/15)
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- (S)-1-Boc-3-hydroxypiperidine synthesis method
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The invention discloses a (S)-1-Boc-3-hydroxypiperidine synthesis method. The method utilizes (R)-glyceraldehyde acetonide as a raw material. Through witting reaction-based acetonitrile group addition, palladium-carbon-based double bond reduction, deprotection, p-tosyl selective addition, Raney nickel-based hydrogenation reduction of the nitrile group along with ring closing, and piperidine ring nitrogen Boc protection, the (S)-1-Boc-3-hydroxypiperidine is obtained. The method utilizes the cheap chiral raw material as a starting material, produces a chiral product and prevents large material consumption and a yield loss of a splitting technology.
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- Concise Enantioselective Synthesis of Naturally Active (S)-3-Hydroxypiperidine
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A short and efficient enantioselective synthesis of natural product (S)-3-hydroxypiperidine has been achieved starting from commercially available raw materials employing two catalytic routes: (i) cocatalyzed hydrolytic kinetic resolution (HKR) of racemic methyl-3-(oxiran-2-yl)propanoate; (ii) proline-catalyzed α-aminooxylation followed by Horner-Wardsworth-Emmons olefination in high enantiomeric purity (97% ee) and high overall yield (38%). (Chemical Equation Presented).
- Dey, Soumen,Karabal, Pratibha U.,Sudalai, Arumugam
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p. 1559 - 1565
(2015/06/02)
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- A practical and enantiospecific synthesis of (-)-(R)- and (+)-(S)-piperidin-3-ols
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A highly enantiospecific, azide-free synthesis of (-)-(R)- and (+)-(S)-piperidin-3-ol in excellent yield was developed. The key step of the synthesis involves the enantiospecific ring openings of enantiomerically pure (R)- and (S)-2-(oxiran-2-ylmethyl)-1H-isoindole-1,3(2H)-diones with the diethyl malonate anion and subsequent decarboxylation.
- Babu, Meruva Suresh,Raghunadh, Akula,Ramulu, Konda,Dahanukar, Vilas H.,Syam Kumar, Unniaran K.,Dubey, P. Kumar
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p. 1507 - 1515
(2015/02/19)
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- Asymmetric syntheses of pyrrolidine and piperidine derivatives Via regio-and stereo-selective ring-opening reactions of chiral aziridine
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Asymmetric synthesis of cyclic β-amino alcohols (pyrrolidine and piperidine derivatives) has been achieved using a chiral aziridine as the starting material. The key step of this synthetic methodology is regio- and stereo-controlled ring-opening of the chiral aziridine with acetic acid or acetyl chloride.
- Higashiyama, Kimio,Matsumura, Masataka,Kurita, Emiko,Yamauchi, Takayasu
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p. 371 - 380
(2013/08/15)
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- Urethane-containing aminosteroid compounds
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Urethane-containing amino steroids having the general chemical formula: STR1 wherein a, b, R1, R2, R3, R4, R14 and Z are as defined in the specification. Also disclosed are pharmaceutical composition and the use of the compounds/composition in the treatment of congestive heart failure.
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- Enantioenriched N-(2-Chloroalkyl)-3-acetoxypiperidines as Potential Cholinotoxic Agents. Synthesis and Preliminary Evidence for Spirocyclic Aziridinium Formation.
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The syntheses of six enantioenriched analogs representing cyclic forms of acetylcholine are reported. (S)- and (R)-N-(2-chloroethyl)-3-acetoxypiperidine and (R,R)-, (R,S)-, (S,R)-, and (S,S)-N-(2-chloropropyl)-3-acetoxypiperidine have been synthesized from (R)- or (S)-3-hydroxypiperidine in five steps. (R)- and (S)-3-hydroxypiperidine were accessed via parallel stereospecific routes from d- and l-glutamic acid, and through fractional recrystallization of diastereomeric tartranilic acid salts. (S)-N-(2-Chloroethyl)-3-acetoxypiperidine was reacted with silver perchlorate to form a spirocyclic aziridinium analog of acetylcholine as evidenced by a characteristic 1H NMR shift for the aziridinium methylene groups.
- Huh, Nam,Thompson, Charles M.
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p. 5935 - 5950
(2007/10/02)
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- Synthesis and pharmacological activity of stereoisomers of 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylic acid methyl 1-(phenylmethyl)-3-piperidinyl ester
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1,4-Dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylic acid methyl 1-(phenylmethyl)-3-piperidinyl ester 1, a highly potent calcium antagonist, was separated into stereo- and optical isomers to investigate the differences of antihypertensive activities between them. Fractional crystallization of the hydrochlorides of 1 gave α- and β-diasterioisomers. The α-isomer (benidipine hydrochloride, KW-3049) showed very strong hypotensive effect, but little activity was observed in the β-isomer. From optically resolved 1,4-dihydro-5-methoxycarbonyl-2,6-dimethyl-4-(3-nitrophenyl)-3-pyridi necarboxylic acids 2, and 1-benzyl-3-piperidinols 3, four optical isomers of 1 were synthesized, and their absolute configurations were deduced. The hypotensive activity of (+)-α, namely (S)-(S)-1, was 30 to 100 times stronger than that of (-)-α in intravenously administered spontaneously hypertensive rats.
- Muto,Kuroda,Kawato,Karasawa,Kubo,Nakamizo
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p. 1662 - 1665
(2007/10/02)
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- REACTIONS OF β-SUBSTITUTED AMINES-IV. KINETICS AND STEREOCHEMISTRY OF THE THERMAL REARRANGEMENT OF (S)-2-CHLOROMETYL-1-ETHYLPYRROLIDINE TO (R)-3-CHLORO-1-ETHYLPIPERIDINE, AND THE STEREO-CHEMICAL COURSE OF THEIR REACTIONS WITH NUCLEOPHILES
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The rate of the thermal rearrangement of (S)-2-chloromethyl-1-ethylpyrrolidine to (R)-3-chloro-1-ethylpiperidine has been examined at three temperatures in benzene by PMR and polarimetry.The rearrangement was shown to be completely stereospecific and to obey a simple first order law.The calculated Ea, ΔH(excit.) and ΔS(excit.) were 22+/-2 kcal/mole (25 deg C), 21+/-2.5 kcal/mole (25 deg C) and -10+/-2 e.u. (0 deg K) respectively.The effect of solvents having differing dielectric constants was also studied.A transition state 9'a and an ion pair intermediate 3a are suggested for the rearrangement.The stereochemical course of the reactions of (S)-1a, (R)-2a and (S)-2a with hydroxide and methoxide ions have been shown to be 100percent stereospecific with an uncertainity of about 1percent.The absolute configurations of all optically active reactants and products were established by chemical correlations with known compounds or by ORD and chemical inference.The ring opening of both the primary and secondary aziridinium ion positions of 1-azonia-1-ethylbicyclohexane by nucleophiles proceeds entirely by SN2 processes.The conversion of (R)-1-ethyl-3-hydroxypiperidine to (S)-2a*HCl with thionyl chloride in chloroform proceeds by inversion with 4.8percent racemization, whereas the thermal rearrangement of (S)-1a to (R)-2a occurs with complete retention of absolute configuration.
- Hammer, Charles F.,Weber, John D.
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p. 2173 - 2180
(2007/10/02)
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