Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides

1998 ◽  
Vol 63 (12) ◽  
pp. 2044-2064 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Milena Masojídková ◽  
Antonín Holý
Keyword(s):  
Allyl Alcohol ◽  
Major Product ◽  
Protecting Groups ◽  
Carbocyclic Nucleosides ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Benzoyl Group ◽  
Glucose Reduction ◽  
Hydroxy Groups

Racemic dimethyl 4-methoxy- (11 and 12), diallyl 4-allyloxy- (13 and 14) and dimethyl 4-(ethylsulfanyl)-2-hydroxycyclopentane-1,1-dicarboxylates (15 and 16) were prepared by base-catalyzed addition of methanol, allyl alcohol and ethylsulfane, respectively, to dimethyl (4-oxobut-2-en-1-yl)malonate (6). Deallylation of 13 and 14 afforded 4-hydroxycyclopentanes 27 and 28. Reduction of 11-16 with lithium aluminium hydride gave the corresponding 4-substituted 2,2-bis(hydroxymethyl)cyclopentanols. Dimethyl (2S,3S,4R)-, (2R,3S,4R)-3-benzyloxy-4-formyloxy-2-hydroxycyclopentane-1,1-dicarboxylates (35, 36) and dimethyl (2S,3S,4R)-, (2R,3S,4R)-3-benzyloxy-2-benzoyloxy-4-methoxycyclopentane-1,1-dicarboxylates (39, 40) were synthesized starting from D-glucose. Reduction of dimethyl cyclopentane-1,1-dicarboxylates 39 and 40 with lithium aluminium hydride, benzoylation of the formed hydroxy derivatives, hydrogenolysis of benzyl groups, conversion of the liberated hydroxy groups into dithiocarbonates and their reduction with tributylstannane afforded, after removal of the protecting groups, (2R,4R)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-2-ol ((2R,4R)-17) and (3R,4R)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-3-ol (51). Reduction of a mixture of esters 35 and 36 gave (2R,3R)-2-benzyloxy-5-(hydroxymethyl)hexane-1,3,6-triol (52) as the major product and (2R,3S,4R)-3-benzyloxy-1,1-bis(hydroxymethyl)cyclopentane-2,4-diol (53) as the minor product. The latter was converted into (3R,4R)-1,1-bis(hydroxymethyl)cyclopentane-3,4-diol (58). 3-Deoxycarba analogues 51 and 58 arose by migration of benzoyl group in the preparation of the dithiocarbonates.

Chemistry of the Podocarpaceae. XXXIV. Some oxidation products of (13R)-Labda-8(17),14-dien-13-ol (Manool)

1971 ◽  
Vol 24 (11) ◽  
pp. 2365 ◽  
Author(s):  
RC Cambie ◽  
KN Joblin ◽  
AF Preston
Keyword(s):  
Nucleophilic Substitution ◽  
Potassium Permanganate ◽  
Hydroxy Acid ◽  
Methyl Ketone ◽  
Major Product ◽  
Oxidation Products ◽  
Lithium Aluminium Hydride ◽  
Methyl Ketones ◽  
Sodium Dichromate ◽  
Lithium Aluminium

Some products from the oxidation of manool (3) are examined. Potassium permanganate gives, inter alia, the hitherto unreported compound (16) while sodium dichromate gives the methyl ketone (5) and, as the major product, a mixture of (Z)- and (E)-α,β-unsaturated aldehydes (21). Hypoiodite oxidation of the methyl ketone (5) gives the α-hydroxy acid (26) in addition to the expected acid (6). Products of nucleophilic substitution have also been obtained from the hypoiodite oxidation of the methyl ketones (9) and (37). Peracid oxidation of the methyl ketone (5) gives the epoxy acetate (41) which, on reduction with lithium aluminium hydride, affords the diol (7), from which the odoriferous oxide (30) can be prepared. Oxidations leading to formation of the dione (10) are investigated.

Chemistry of the Podocarpaceae. XXII. Aspects of the chemistry of Totara-8,11,13-trien-13-ol

1969 ◽  
Vol 22 (9) ◽  
pp. 1975 ◽  
Author(s):  
RC Cambie ◽  
DR Crump ◽  
RN Duve
Keyword(s):  
Sulphuric Acid ◽  
Methyl Ether ◽  
Major Product ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Birch Reduction ◽  
Transannular Cyclization ◽  
Lithium Aluminium ◽  
Fragmentation Reactions

Attempts have been made to effect fragmentation reactions with bromo- tetralone systems related to 6α-bromo-13-hydroxytotara-8,11,13-trien-7- one (VII), a compound which affords a secoditerpenoid (IX) when treated with DMSO-NaHCO3. On treatment with sulphuric acid in acetone, the mono- epoxide derivative (XXVIII) of the methyl ether of the secoditerpenoid undergoes a novel aromatization to a naphthalenic aldehyde (XXXI) by successive transannular cyclization and fragmentation reactions. ��� A 7β-hydroxy configuration has been confirmed for the major product from reduction of 13-acetoxytotara-8,11,13-trien-7-one (VIII) with lithium aluminium hydride. 13-Methoxytotara-8,11,13-triene (II) has been deisopropylated and then subjected to Birch reduction in an attempt to effect a high yield conversion into (+)-podocarp-8(14)-en- 13-one (XXXVII), a potentially useful intermediate for synthesis.

scholarly journals Study of lithium aluminium hydride reduction of 5-acetyl-1,6-dimethyl-4-phenyl-3,4-dihydropyrimidin-2(1h)-one

2017 ◽  
Vol 15 (1) ◽  
pp. 17-22
Author(s):  
Dragan Zlatkovic ◽  
Niko Radulovic
Keyword(s):  
Chromatographic Separation ◽  
Major Product ◽  
Lithium Aluminium Hydride ◽  
Reaction Products ◽  
Hydride Reduction ◽  
Lithium Aluminium

In this paper, we investigated the LiAlH4-reduction of 5-acetyl-1,6-dimethyl- 4-phenyl-3,4-dihydropyrimidin-2(1H)-one (N-methylated Biginelli compound). Following the reduction and SiO2-promoted dehydration, (Z)-5-ethylidene-1-methyl-6- methylene-4-phenyltetrahydropyrimidin-2(1H)-one was isolated as the major product (33% yield). Chromatographic separation of the reaction products also allowed us to isolate (yield in parentheses) and fully spectrally characterize: 1,6-dimethyl-4-phenyl- 5-vinyl-3,4-dihydropyrimidin-2(1H)-one (20%), 5-ethyl-1,6-dimethyl-4-phenyl-3,4- dihydro-pyrimidin-2(1H)-one (9%), 5-(1-hydroxyethyl)-1,6-dimethyl-4-phenyl-3,4- dihydropyrimidin-2(1H)-one (5%). A possible mechanism explaining the formation of these products is proposed.

Synthesis of racemic and optically active erythro- and threo-9-(2,3,4-trihydroxybutyl)adenines and related compounds

1979 ◽  
Vol 44 (2) ◽  
pp. 593-612 ◽  
Author(s):  
Antonín Holý
Keyword(s):  
Sodium Borohydride ◽  
Sodium Salt ◽  
Sodium Periodate ◽  
Optically Active ◽  
Protecting Groups ◽  
Lithium Aluminium Hydride ◽  
Acidic Hydrolysis ◽  
Lithium Aluminium ◽  
Hydrolysis Of ◽  
Related Compounds

Reduction of diethyl 2,3-O-isopropylidene-DL-tartrate (II) with lithium aluminium hydride afforded 2,2-dimethyl-1,3-dioxolane-threo-4,5-dimethanol (III) which was transformed to the monotosyl derivative VI. Reaction of this compound with sodium salt of adenine, followed by acidic deblocking, gave 9-(DL)-threo-(2,3,4-trihydroxybutyl)adenine (IX). Analogously, 9-(DL)-erythro-(2,3,4-trihydroxybutyl)adenine (XVII) was prepared from diethyl meso-tartrate (XI) via the diol XIII and the tosyl derivative XV. 1,3-O-Benzylidene-D-threitol (D-XVIII) was converted successively into the 4-O-tosyl derivative XIX and the 2-O-benzoyl-4-O-tosyl derivative XX. Reaction of the compound XX with sodium salt of adenine, followed by removal of the protecting groups in the intermediate XXI, afforded 9-(D)-threo-(2,3,4-trihydroxybutyl)adenine (D-XXII); analogously, 1,3-O-benzylidene-L-threitol (L-XVIII) was transformed into the 9-(L)-threo-derivative L-XXII. The D-threo-derivative D-XXII was prepared also from 5-O-tosyl-3-O-benzoyl-1,2-O-isopropylidene-α-D-xylofuranoside (XXIII) or from 3-O-benzyl derivative XXIX by condensation with sodium salt of adenine, followed by acidic hydrolysis, degradation of the 1,2-diol grouping by sodium periodate and sodium borohydride, and methanolysis or hydrogenolysis. An analogous procedure was used for preparation of 1-(D)-threo-(2,3,4-trihydroxybutyl)uracil (D-XXVII). Methyl 2,3-O-isopropylidene-5-benzoyl-6-tosyl-D-mannofuranoside (XXXVI) was transformed to the 5-(adenin-9-yl) derivative XXXVII which after hydrolysis of the dioxolane ring, followed by cleavage of the cis-diol with sodium periodate, reduction with sodium borohydride and methanolysis, afforded 9-(D)-erythro-(2,3,4-trihydroxybutyl)adenine (D-XL). The L-enantiomer (L-XL) was obtained from 5-O-(adenin-9-yl)-3-O-benzoyl-1,2-O-isopropylidene-β-L-arabinofuranoside (XXXIIIb) by acidic cleavage, degradation of the intermediate XXXIV with periodate and methanolysis.

Pinching group stabilization. The synthesis and thermal isomerization of 10-Oxapentacyclo[6.3.2.13,6.01,8.02,7]tetradeca-4,12-diene

1984 ◽  
Vol 37 (6) ◽  
pp. 1293 ◽  
Author(s):  
DN Butler ◽  
RA Russell ◽  
RB Waring ◽  
RN Warrener
Keyword(s):  
Cyclic Ether ◽  
Major Product ◽  
The Novel ◽  
Lithium Aluminium Hydride ◽  
Group Effect ◽  
Flash Vacuum Pyrolysis ◽  
Lithium Aluminium ◽  
Vacuum Pyrolysis ◽  
Site Selective ◽  
Dimethyl Benzene

Sensitized irradiation (benzophenone, 0�, N2, pyrex filter, medium pressure Hg lamp) of dimethyl tricyclo[4.2.1.02,5]nona-3,7-diene-3,4-dicarboxylate (11) in (E)-1,2-dichloroethene yielded a mixture of 1 : 1 adducts (13) and (14) by site selective [2 π+2 π] cycloaddition at the cyclobutene π-bond. Reduction of the (Z)-dichloro isomer(13) with lithium aluminium hydride formed the related diol (16) which is the immediate precursor to the cyclic ether (18). Dechlorination of (18) with zinc in ethanol forms the title diene (19). Thermolysis of the polycyclic diester (20) affords the fragmentation products cyclopentadiene and dimethyl benzene-1,4-dicarboxylate. In contrast, the title compound (19) containing the cyclic ether ring was more stable and yielded the novel isomer (28) as the major product only upon flash vacuum pyrolysis at 560�(1.5 × 10-2 Torr). This difference in behaviour is attributed to a pinching group effect exerted by the cyclic ether present in (19).

Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)hexopyranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides

2001 ◽  
Vol 66 (5) ◽  
pp. 785-798 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Antonín Holý
Keyword(s):  
Sodium Salt ◽  
Diethyl Malonate ◽  
Carbocyclic Nucleosides ◽  
Lithium Aluminium Hydride ◽  
Dimethyl Malonate ◽  
Lithium Aluminium

3-O-Benzyl-1,2-O-isopropylidene-α-D-glucofuranose-5,6-O-sulfate (1) was treated with sodium salt of dimethyl malonate to obtain, after hydrolysis, methyl 5-(3-O-benzyl-1,2-O-isopropylidene-α-D-erythrofuranos-4-yl)-2-oxotetrahydrofuran-3-carboxylate (3) which was converted to the mixture of methyl (2S,3R,4R)- (7) and (2R,3R,4R)-2-(acetyloxy)-3-(benzyloxy)-4-(formyloxy)-7-oxo-6-oxabicyclo[3.2.1]octane-1-carboxylate (8). The compound 7 was reduced with lithium aluminium hydride to give (1R,2R,3R,4S)-3-(benzyloxy)-5,5-bis(hydroxymethyl)cyclohexane-1,2,4-triol (9) which was transformed to (1R,2S,4R)-5,5-bis(hydroxymethyl)cyclohexane-1,2,4-triol (14). Treatment of sodium salt of diethyl malonate with 3-O-benzyl-5,6-dideoxy-6-iodo-1,2-O-isopropylidene-α-D-xylo-hexofuranose (19) gave diethyl (3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranos-6-yl)malonate (20) which was converted to (1R,3R)-4,4-bis(hydroxymethyl)cyclohexane-1,3-diol (28) by a similar procedure to that used for 14.

The radiosynthesis of No-carrier added [1-11C]allyl alcohol evidence for the formation of a new reducing species: Lithium aluminium hydride - vinylmagnesium bromide

1994 ◽  
Vol 34 (12) ◽  
pp. 1165-1174
Author(s):  
Marie-Claire Lasne ◽  
Bernard Moreau ◽  
Philippe Cairon ◽  
Louisa Barré
Keyword(s):  
Allyl Alcohol ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
No Carrier Added

The application of lithium aluminium hydride to the preparation of some amino-alkanols

1951 ◽  
Vol 1 (10) ◽  
pp. 469-472
Author(s):  
A. W. D. Avison
Keyword(s):  
Lithium Aluminium Hydride ◽  
Lithium Aluminium

Convenient Synthesis of (Z)-7- and (E)-9-dodecene-1-yl Acetate, Components of Some Lepidoptera Insect Sex Pheromone

2017 ◽  
Vol 68 (1) ◽  
pp. 180-185
Author(s):  
Adriana Maria Andreica ◽  
Lucia Gansca ◽  
Irina Ciotlaus ◽  
Ioan Oprean
Keyword(s):  
Sex Pheromone ◽  
Coupling Reaction ◽  
Coupling Scheme ◽  
Lithium Aluminium Hydride ◽  
Terminal Alkyne ◽  
Mercury Derivative ◽  
Lithium Aluminium ◽  
Convenient Synthesis ◽  
Practical Synthesis ◽  
Insect Sex

Were developed new and practical synthesis of (Z)-7-dodecene-1-yl acetate and (E)-9-dodecene-1-yl acetate. The routes involve, as the key step, the use of the mercury derivative of the terminal-alkyne w-functionalised as intermediate. The synthesis of (Z)-7-dodecene-1-yl acetate was based on a C6+C2=C8 and C8+C4=C12 coupling scheme, starting from 1,6-hexane-diol. The first coupling reaction took place between 1-tert-butoxy-6-bromo-hexane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-oct-7-yne, which is transformed in di[tert-butoxy-oct-7-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromobutane obtaining 1-tert-butoxy-dodec-7-yne. After acetylation and reduction with lithium aluminium hydride of 7-dodecyne-1-yl acetate gave (Z)-7-dodecene-1-yl acetate with 96 % purity. The synthesis of (E)-9-dodecene-1-yl acetate was based on a C8+C2=C10 and C10+C2=C12 coupling scheme, starting from 1,8-octane-diol. The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromoethane obtaining 1-tert-butoxy-dodec-9-yne. After reduction with lithium aluminium hydride of 1-tert-butoxy-(E)-9-dodecene and acetylation was obtained (E)-9-dodecene-1-yl acetate with 97 % purity.

3-(s-Hydrindacen-4-yl)propylamines and 4-(s-hydrindacen-4-yl)butylamines; Synthesis and pharmacological screening

1981 ◽  
Vol 46 (8) ◽  
pp. 1800-1807 ◽  
Author(s):  
Zdeněk Vejdělek ◽  
Marie Bartošová ◽  
Miroslav Protiva
Keyword(s):  
Malonic Acid ◽  
Local Anaesthetics ◽  
Lithium Aluminium Hydride ◽  
Spasmolytic Activity ◽  
Lithium Aluminium ◽  
Malonic Acid Derivatives ◽  
Pharmacological Screening ◽  
Hydroxyethyl Piperazine

4-Chloromethyl-s-hydrindacene (VIIa) was transformed via the malonic acid derivatives VIIIa and IXa to the acid Xb which afforded in four steps the homological acid Xc. Reactions of chlorides of both acids (XIbc ) with dimethylamine, 1-methylpiperazine and 1-(2-hydroxyethyl)piperazine led to the amides XIIbc-XIVbc which were reduced with lithium aluminium hydride to the title compounds IVcd-VIcd. The amines obtained show central neuroleptic effects only in subtoxic doses; they are also potent local anaesthetics and have significant spasmolytic activity of the neurotropic as well as musculotropic type.

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