189625-14-7Relevant academic research and scientific papers
Method for preparing (1R, 3S)-3-aminocyclopentanol hydrochloride
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Paragraph 0030; 0037-0039; 0049-0053, (2021/03/31)
The invention discloses a method for preparing (1R, 3S) 3-aminocyclopentanol hydrochloride, belongs to the field of organic chemical synthesis, and provides a process route to overcome the defects ofhigh price, difficulty in chiral control and the like in the prior art. The process route comprises the following steps: 1) oxidizing tert-butyl carbonate hydroxylamine into tert-butyl carbonate nitrosyl under the catalysis of copper chloride and 2-ethyl-2-oxazoline, then carrying out a hetero Diels-Alder reaction with cyclopentadiene in situ; 2) selectively reducing nitrogen-oxygen bonds in a zinc powder-acetic acid reaction system; 3) under the catalysis of lipase, reacting with vinyl acetate to optically and selectively realize chiral resolution; 4) reducing double bonds through palladium carbon hydrogenation; 5) under the alkaline condition of lithium hydroxide-methanol, performing deacetylation protection; and 6) removing tert-butyl carbonate protection in a hydrogen chloride isopropanol acid solution prepared from acetyl chloride and isopropanol in situ, and forming hydrochloride in situ to obtain a target product. The synthetic method has the beneficial effects that the synthetic method has the characteristics of novel and short route, high optical purity, low cost and the like.
Enantioselective syntheses of carbocyclic nucleosides 5′- homocarbovir, epi-4′-homocarbovir, and their cyclopropylamine analogs using facially selective Pd-mediated allylations
Tardibono Jr., Lawrence P.,Miller, Marvin J.,Balzarini, Jan
, p. 825 - 829 (2011/03/19)
Carbocyclic nucleosides (-)-5′-homocarbovir and (+)-epi-4′- homocarbovir were prepared from an acylnitroso-derived hetero Diels-Alder cycloadduct. A kinetic enzymatic resolution generated an enantiopure aminocyclopentenol and Pd(0)-mediated decarboxylativ
Total synthesis of (-)-agelastatin A
Yoshimitsu, Takehiko,Ino, Tatsunori,Tanaka, Tetsuaki
supporting information; experimental part, p. 5457 - 5460 (2009/06/06)
(Chemical Equation Presented) A new route to (-)-agelastatin A is reported. The requisite nitrogen functionalities of the agelastatin core have been installed by intramolecular aziridination of an azidoformate and subsequent regioselective azidation, lead
Concise syntheses of enantiomerically pure protected 4-hydroxypyroglutamic acid and 4-hydroxyproline from a nitroso-cyclopentadiene cycloadduct
Huang, Weiqiang,Miller, Marvin J.
experimental part, p. 2835 - 2838 (2009/06/28)
O-TBS-protected methyl trans-4-hydroxypyroglutamate and methyl trans-4-hydroxyproline ester were synthesized from nitroso-cyclopentadiene Diels-Alder cycloadducts. Enzymatic resolution of the key intermediate, 4-amino-cyclopent-2-enol, provides access to both l- and d-amino acids.
Chemoenzymatic asymmetric total synthesis of phosphodiesterase inhibitors: Preparation of a polycyclic pyrazolo[3,4-d]pyrimidine from an acylnitroso Diels-Alder cycloadduct-derived aminocyclopentenol
Jiang, May Xiao-Wu,Warshakoon, Namal C.,Miller, Marvin J.
, p. 2824 - 2827 (2007/10/03)
(Chemical Equation Presented) Enzymatic resolution of Boc-protected 4-aminocyclopenten1-ol 4c gave both enantiomers 5c and 6c in high ee. Boc removal and separate condensation with chloropyrazolopyrimidine 18 provided elaborated 1,4-aminocyclopentenol derivatives 20 and 26, respectively. Separate treatment of 20 and 26 with Pd(0) under basic conditions induced cyclization to unsaturated polycycles 22 and 27, which, upon catalytic hydrogenation, were transformed to new cyclopentane-containing pyrazolopyrimidines 24 and 28, analogues of recently described novel phosphodiesterase inhibitors.
IMPROVEMENTS IN PHARMACEUTICALLY USEFUL COMPOUNDS
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Page 42, (2010/11/30)
A compound of formula (I) or (II): wherein A is hydrogen or CR1R2; Y and Z are each, independently, hydrogen or a halogen;X is -NR4R5, or R7; R1 is hydrogen, or a substituted or unsubstituted alkyl or alkenyl group containing 1-4 carbon atoms; when X is -NR4R5, R2 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, aralkyl aralkenyl, or aralkynyl group, that optionally includes at least one heteroatom in its carbon skeleton and contains 1-12 carbon atoms; when X is R7, R2 is an unsubstituted alkyl, alkenyl or alkynyl group, or a substituted or unsubstituted aryl, aralkyl aralkenyl, or aralkynyl group, that optionally includes at least one heteroatom in its carbon skeleton and contains 1-12 carbon atoms; R3 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, aralkyl aralkenyl, or aralkynyl group, that optionally includes at least one heteroatom in its carbon skeleton and contains 1-12 carbon atoms; R4 is hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, aralkyl aralkenyl, or aralkynyl group, that optionally includes at least one heteroatom in its carbon skeleton and contains 1-12 carbon atoms, -COOR8, or -COR8; R5 is hydrogen, or a substituted or unsubstituted alkyl or alkenyl group containing 1-5 carbon atoms; R7 is an unsubstituted alkyl, alkenyl, or alkynyl group, that contains 1-4 carbon atoms; and, R8 is an unsubstituted or halo-substituted alkyl, aryl, or aralkyl group, that contains 1-12 carbon atoms.
Synthesis of 4-azacyclopent-2-enones and 5,5-dialkyl-4-azacyclopent-2- enones
Dauvergne, Jér?me,Happe, Alan M.,Jadhav, Vasudev,Justice, David,Matos, Marie-Christine,McCormack, Peter J.,Pitts, Michael R.,Roberts, Stanley M.,Singh, Sanjay K.,Snape, Timothy J.,Whittall, John
, p. 2559 - 2567 (2007/10/03)
Three different methods are reported for the preparation of 4-azacyclo-2-enones 1, two of which allow the preparation of the compounds in optically active form. In addition, a facile route to 4-aza-5,5- dimethylcyclopent-2-enones 2 is disclosed.
Chemoenzymatic synthesis and synthetic application of enantiopure aminocyclopentenols: Total synthesis of carbocyclic (+)-uracil polyoxin C and its α-epimer
Li, Fangzheng,Brogan, John B.,Gage, Jennifer L.,Zhang, Deyi,Miller, Marvin J.
, p. 4538 - 4540 (2007/10/03)
Carbocyclic uracil polyoxin C (+)-2 and its α-epimer (-)-3 were synthesized in an efficient fashion from cis-4-(N-tert-butylcarbamoyl)cyclopent- 2-en-1-ol (±)-7. The synthesis incorporates a concise, inexpensive chemoenzymatic synthesis of enantiopure ami
Synthetic application of acylnitroso Diels-Alder derived aminocyclopentenols: Total synthesis of (+)-streptazolin
Li, Fangzheng,Warshakoon, Namal C.,Miller, Marvin J.
, p. 8836 - 8841 (2007/10/03)
Concise total syntheses of (+)-streptazolin 1 and its more stable dihydro derivative 2 were accomplished via an intramolecular aldol condensation strategy starting from readily available aminocyclopentenol (-)-7. The synthetic sequence included reductive amination, stereoselective epoxidation, intramolecular aldol (and condensation) reaction, and Wittig reaction. The overall yield for dihydro derivative 2 from aminocyclopentenol (-)-7 was about 7% for a total of 14 steps.
Enzymatic resolution of aminocyclopentenols as precursors to D- and L- carbocyclic nucleosides
Mulvihill,Gage,Miller
, p. 3357 - 3363 (2007/10/03)
Racemic cis-4-aminocyclopent-2-en-1-ols were synthesized in three steps utilizing hetero Diels-Alder chemistry. Starting from suitably protected hydroxylamines, oxidization with sodium periodate and trapping with cyclopentadiene afforded cycloadducts (±)-5a-d. The N-O bond of the cycloadducts was reduced with Mo(CO)6 to afford (±)-cis-4-aminocyclopent- 2-en-1-ols (±)-6a-d. These compounds, or their corresponding acetates, were kinetically resolved by enzymatic acetylation of hydrolysis, respectively. Enzymatic acetylation of cis-N-(benzylcarbamoyl)-4-aminocylopent-2-enol [(±)-6a] with Candida antarctica B lipase and Pseudomonas species lipase gave the corresponding acetate (-)-7a in 90% and 92% ee, respectively, after 40% conversion. Enzymatic hydrolysis of cis-N-acetyl-4-aminocyclopent-2-enol 1-O-acetate (±)-7d with electric eel acetylcholine esterase was successful in providing both cis-N-acetyl-4-aminocyclopent-2-enols (+)-6d and (+)-7d in 92% ee (99% ee after a single recrystallizaton) after 40% conversion. Further synthetic transformation of these resolved synthetic building blocks and derivatives are also reported.
