33451-05-7Relevant academic research and scientific papers
The Synthesis of Chiral Allyl Carbamates via Merger of Photoredox and Nickel Catalysis
Garbacz, Mateusz,Stecko, Sebastian
, p. 3213 - 3222 (2020/07/06)
A mild, and versatile, organophotoredox/Ni-mediated protocol was developed for the direct preparation of diverse, enantioenriched allyl carbamates. The reported approach represents a significant departure from classical step-by-step synthesis of allyl carbamates. This dual photoredox/Ni based strategy offers unrivalled capacity for convergent unification of readily available alkyl halides and chiral carbamates derived from 1-bromo-alken-3-ols with high chemoselectivity and efficiency. The reported photoredox/Ni catalyzed cross-coupling reaction is not limited to carbamates, but also to other O-derivatives such as esters, ethers, acetals, carbonates or silyl ethers. To demonstrate the utility of the reported protocol, the resulting allyl carbamates were transformed into functionalized non-racemic allylamines through a sigmatropic rearrangement reaction in enantiospecific manner. This approach allowed for synthesis of enantiomeric allylamines by a simple control of the geometry of a double bond of allyl carbamates. (Figure presented.).
Method for preparing eight-membered heterocyclic alkyne
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Paragraph 0035-0037, (2019/11/13)
The invention belongs to the field of organic synthesis and relates to a method for preparing an eight-membered-ring alkyne having a chemical formula shown in the description, with Ts being p-tosyl. The method includes (a) substituting hydroxy in a compou
A biological orthogonal experiment mark [...] intermediate hydroxy derivative synthesis method (by machine translation)
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Paragraph 0014; 0018; 0023, (2018/10/19)
The invention relates to a biological orthogonal experiment mark [...] intermediate hydroxy derivative synthesis method, comprising the following steps: (a) the O-methanol, dichloromethane, imidazole-butyl dimethylchlorosilane mixed for reaction; over the chromatographic column purification to obtain compound II; (b) adding toluene sulfonyl amino methyl formate, triphenylphosphine and azo-phthalic acid diethyl ester reaction, after concentrating column purification to obtain compound III; (c) the compound III is dissolved in the methanol, lowering the temperature to ≤ 0 °C, adding potassium carbonate by the reaction of, water quenching; (d) and condensing the chromatographic column purification to obtain compound V; (e) the compound V soluble in tetrahydrofuran, add tetrabutyl ammonium fluoride solution reaction, water quenching; and condensing the chromatographic column purification to obtain compound VI. The aromatic eight-membered ring mark [...] intermediate of the synthetic route re-design. (by machine translation)
Synthesis method of biological orthogonal experiment aromatic eight-membered ring marker
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Paragraph 0025, (2018/12/02)
The invention relates to a synthesis method of a biological orthogonal experiment aromatic eight-membered ring marker. The synthesis method comprises the following steps: (a) after mixing benzenedimethanol, dichloromethane, imidazole and tert-butyldimethylsilane, reacting; carrying out chromatographic column purification to obtain a compound II; (b) adding toluenesulfonyl methyl carbamate, triphenylphosphine and diethyl azodicarboxylate and reacting; after concentrating, carrying out column purification to obtain a compound III; (c) dissolving the compound III in methanol and cooling until thetemperature is less than or equal to 0 DEG C; then adding potassium carbonate and reacting; adding water and quenching; (d) after extracting with ethyl acetate for a plurality of times, combining organic phases and purifying to obtain a compound V; (e) concentrating and carrying out chromatographic column purification to obtain a compound VI; (f) after concentrating, carrying out chromatographiccolumn purification to obtain a compound VII; (g) after concentrating, carrying out chromatographic column purification to obtain a compound I. By adopting the synthesis method, a redesign of a synthesis route of the aromatic eight-membered ring marker is realized.
Synthetic method for ring formation intermediate of aromatic octatomic ring through biological orthogonal experiment
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Paragraph 0019; 0024; 0028-0031, (2019/01/06)
The invention relates to a synthetic method for a ring formation intermediate of an aromatic octatomic ring through a biological orthogonal experiment. The synthetic method comprises the following steps: (a) mixing o-benzenedicarbinol, dichloromethane, imidazole and tert-butyldimethylsilyl chloride for reaction, and purifying by virtue of a chromatographic column, so as to obtain a compound II; (b) adding methyl toluenesulfonyl carbamate, triphenylphosphine and diethyl azodicarboxylate, concentrating, and carrying out column purification, so as to obtain a compound III; (c) dissolving the compound III into methanol, cooling to the temperature less than or equal to 0 DEG C, adding potassium carbonate for reaction, and adding water for quenching; (d) carrying out extraction for several timesby virtue of ethyl acetate, combining organic phases, drying by virtue of anhydrous sodium sulfate, concentrating, and purifying by virtue of the chromatographic column, so as to obtain a compound V;(e) concentrating, and purifying by virtue of the chromatographic column, so as to obtain a compound VI; and (f) concentrating, and purifying by virtue of the chromatographic column, so as to obtaina compound VII. According to the synthetic method, the redesign of a synthetic route for the ring formation intermediate of the aromatic octatomic ring is realized.
Synthesis, characterization and structures of cyclic organorhodium complexes of the type [Rh{CH(SO2Ph)CH2CH 2YR2-κC,κY}L2] (YR2 = PPh2, NMe2; L2 = diphosphine, cyclooctadiene)
Block, Michael,Wagner, Christoph,Gomez-Ruiz, Santiago,Steinborn, Dirk
supporting information; body text, p. 4636 - 4646 (2010/08/21)
Reactions of dinuclear chloridorhodium(i) complexes [(RhL2) 2(μ-Cl)2] (L2 = PP: Me2P(CH 2)2PMe2, dmpe, 7a; Ph2PCH 2PPh2, dppm, 7b; Ph2P(CH2) 2PPh2, dppe, 7c; Ph2P(CH2) 3PPh2, dppp, 7d; L2 = cycloocta-1,5-diene, cod, 5) with lithiated γ-phosphino- and γ-aminofunctionalized propyl phenyl sulfones (Li[CH(SO2Ph)CH2CH2PPh 2], 2; Li[CH(SO2Ph)CH2CH2NMe 2], 4) led to the formation of organorhodium inner complexes of the type [Rh{CH(SO2Ph)CH2CH2PPh2- κC,κP}(PP)] (8a-d), [Rh{CH(SO2Ph)CH2CH 2NMe2-κC,κN}(PP)] (9a-d), [Rh{CH(SO 2Ph)CH2CH2PPh2-κC,κP} (cod)]·LiCl (11·LiCl) and [Rh{CH(SO2Ph)CH 2CH2NMe2-κC,κN}(cod)]·LiCl (12·LiCl), respectively. Single-crystal X-ray diffraction analysis of 9c·THF, 11 and 12 exhibited in all three compounds a distorted square planar coordination of the rhodium atoms having bidentately coordinated neutral co-ligands (cod, 11, 12; dppe, 9c) and anionic α-phenylsulfonyl γ-phosphinopropyl (κC,κP; 11) and γ-aminopropyl ligands (κC,κN; 12, 9c), thus being typical organorhodium inner complexes. Furthermore, organorhodium inner complexes of type 8 were obtained in reactions of the dinuclear chloridobridged rhodium complexes [(RhL2) 2(μ-Cl)2] (L2 = PP, 7a-d; cod, 5; (C 2H4)2, 6) with the (non-lithiated) γ-phosphinofunctionalized propyl phenyl sulfone PhSO2CH 2CH2CH2PPh2 (1) resulting in the formation of complexes having the sulfone κP coordinated ([RhClL 2(Ph2PCH2CH2CH2SO 2Ph-κP)] (L2 = PP, 10a-d; cod, 13; (C 2H4)2, 14) which were deprotonated (10a-d, 13) at the α-C atom with lithium diisopropyl amide (LDA) in a subsequent reaction. Single-crystal X-ray diffraction analysis of 10c (PP = dppe) revealed the expected square-planar coordination geometry of Rh. The identities of all rhodium complexes have been unambiguously proved by microanalyses and NMR spectroscopy (1H, 13C, 31P).
OXAZOLE AND THIAZOLE DERIVATIVES AND THEIR USES 2
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Page/Page column 45-46, (2008/12/08)
Compounds of formula (I): wherein A, X, R1, R2, R3, R4, R5, R6 and R8 are as defined in the Specification are useful in the treatment of diseases where enhanced M3 receptor activ
