A simple synthesis of (±)-1,2,3,6-tetrahydro-2,3′-bipyridine (anatabine) and (±)-3-(2-piperidinyl)pyridine (anabasine) from lithium aluminum hydride and pyridine

1997 ◽  
Vol 75 (6) ◽  
pp. 616-620 ◽  
Author(s):  
Chi-Ming Yang ◽  
Dennis D. Tanner
Keyword(s):  
Catalytic Hydrogenation ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Simple Synthesis ◽  
Lithium Aluminum ◽  
Pyridine Solution ◽  
Hydrolysis Of

The hydrolysis of a pyridine solution of lithium tetrakis(N-dihydropyridyl)aluminate (LDPA), which was prepared at 0 °C, yields a mixture of 1,4-, 1,2-, and 2,5-dihydropyridines (DHPs) in a ratio of 26:37:38. The subsequent reversible base-catalyzed condensation of a 1:1 mixture of 1,2- and 2,5-DHPs carried out in the presence of oxygen affords an 89% yield of (±)-anatabine. When the reaction mixture is allowed to stand in the presence of oxygen, anabasine is slowly formed from anatabine by the reaction of the residual DHPs. Anatabine can also be converted into (±)-anabasine by catalytic hydrogenation. Keywords: lithium aluminum hydride, pyridine, anatabine, anabasine.

PSEUDACONITINE, AND THE STEREOCHEMICAL RELATIONSHIP OF THE HIGHLY OXYGENATED ACONITE ALKALOIDS

1963 ◽  
Vol 41 (6) ◽  
pp. 1485-1489 ◽  
Author(s):  
Y. Tsuda ◽  
Léo Marion
Keyword(s):  
Acetic Acid ◽  
Absolute Configuration ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reduction Product ◽  
Lithium Aluminum ◽  
Partial Hydrolysis ◽  
Previous Knowledge ◽  
Relationship Of ◽  
Hydrolysis Of

An alkaloid isolated from Aconitum spicatum Stapf has been found to be identical not only with the originally described pseudaconitine but also with 'α-pseudaconitine'. The product of the partial hydrolysis of the base, i.e., veratroylpseudaconine, is dextrorotatory, and not laevorotatory as recorded in the old literature. On heating, pseudaconitine undergoes pyrolysis, loses the elements of acetic acid, and gives rise to pyropseudaconitine. This substance, on treatment with lithium aluminum hydride, is converted to demethoxyisopyropseudaconine which is identical with the Wolff–Kishner reduction product of pyraconine. This correlation establishes that pseudaconitine and aconitine possess the same absolute configuration, which, in the light of previous knowledge, is extended also to indaconitine, delphinine, mesaconitine, and jesaconitine.

Synthesis and Kinase Phosphorylation of 4-Deoxy-D-threohexulose

1973 ◽  
Vol 51 (7) ◽  
pp. 969-972 ◽  
Author(s):  
Clifford Raymond Haylock ◽  
Keith Norman Slessor
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Kinetic Studies ◽  
Lithium Aluminum ◽  
Substrate Complex ◽  
Acetobacter Suboxydans ◽  
Enzyme Substrate ◽  
Kinase Phosphorylation ◽  
Hydrolysis Of ◽  
Yeast Hexokinase

Synthesis of the only unknown deoxyfructose, 4-deoxy-D-threohexulose, is reported. Its preparation involved reductive lithium aluminum hydride ring opening of 3,4-anhydro-1,2:5,6-di-O-isopropylidene- D-talitol, followed by hydrolysis of the resulting epimeric deoxy diisopropylidene hexitols and selective Acetobacter suboxydans oxidation of 3-deoxy-D-arabinohexitol. Kinetic studies using 4-deoxy-D-threohexulose as substrate for yeast hexokinase support the premise that the C-4 hydroxyl is a binding group in formation of the enzyme–substrate complex. Enzymatic synthesis of 4-deoxy-D-threohexulose 6-phosphate and 4-deoxy-D-threohexulose 1,6-diphosphate has been achieved in low yield from 4-deoxy-D-threohexulose.

Lithium Aluminum Hydride Reactions in Pyridine Solution. IV. Metalation of Di- and Triarylmethanes1

1962 ◽  
Vol 27 (7) ◽  
pp. 2383-2387 ◽  
Author(s):  
Peter T. Lansbury ◽  
Roosevelt Thedford
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Pyridine Solution

Total Synthesis of DL-Glucose, 3-O-Methyl-DL-glucose, and 3-Deoxy-DL-ribo-hexopyranose from 1,6:3,4-Dianhydro-β-DL-allo-hexopyranose, a Product Obtained from Acrolein Dimer

1971 ◽  
Vol 49 (20) ◽  
pp. 3342-3347 ◽  
Author(s):  
U. P. Singh ◽  
R. K. Brown
Keyword(s):  
Total Synthesis ◽  
Acid Hydrolysis ◽  
Sodium Methoxide ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Barium Hydroxide ◽  
Lithium Aluminum ◽  
Methyl Glycoside ◽  
Acid Catalyzed ◽  
Hydrolysis Of

The reaction of butyllithium in ether with 1,6:2,3-dianhydro-4-deoxy-β-DL-ribo-hexopyranose (1), a substance obtained in five steps from acrolein dimer, gave 1,6-anhydro-3,4-dideoxy-β-DL-erythro-hex-3-enopyranose (2). The compound 1,6:3,4-dianhydro-β-DL-allo-hexopyranose (3), obtained from 2, was converted by reaction with aqueous barium hydroxide followed by hydrolysis of the product, to DL-glucose 5. Treatment of 3 with sodium methoxide in methanol followed by acid hydrolysis of the 1,6-anhydro intermediate 6, gave 3-O-methyl-DL-glucose (7). The same intermediate, 6, along with the methyl glycoside 8, could be obtained by the acid-catalyzed reaction of 3 with methanol. Lithium aluminum hydride reacted with 3 to form 1,6-anhydro-3-deoxy-β-DL-ribo-hexopyranose (9), which was hydrolyzed readily to 3-deoxy-DL-ribo-hexopyranose (10).Yields were excellent throughout. All products obtained from the oxirane 3 were those resulting only from trans diaxial opening of the oxirane ring.

STEROIDS: PART II. 6-AMINO STEROIDS

1960 ◽  
Vol 38 (6) ◽  
pp. 981-986 ◽  
Author(s):  
Barbara G. Ketcheson ◽  
Alfred Taurins
Keyword(s):  
High Pressure ◽  
Acetic Acid ◽  
Acid Medium ◽  
Catalytic Hydrogenation ◽  
Acid Treatment ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Acetic Acid Medium ◽  
Propyl Alcohol

Reduction of methyl 3β-acetoxy-6-oximinodinorcholanate using sodium in n-propyl alcohol, and acetylation, gave 6α-acetamido-3β-acetoxydinorcholanic acid; treatment with lithium aluminum hydride in tetrahydrofuran provided 3β,22ξ-dihydroxydinorcholan-6-one. High-pressure hydrogenation of methyl 3β-acetoxy-6-nitro-5-dinorcholenate, using palladium black as catalyst in acetic acid medium, afforded methyl 6ξ-acetamido-3β-acetoxy-5α-dinorcholanate. Under identical conditions, catalytic hydrogenation of 3β-acetoxy-6-nitro-5-cholestene resulted in the formation of 6β-acetamido-3β-acetoxy-5α-cholestane and 6ξ-acetamido-3β-acetoxy-5β-cholestane.

Lithium Aluminum Hydride Reactions in Pyridine Solution. II. The Role of Steric Effects in the Reductive Cleavage of Pinacolones

1961 ◽  
Vol 26 (7) ◽  
pp. 2277-2280 ◽  
Author(s):  
PETER T. LANSBURY ◽  
JOHN R. ROGOZINSKI ◽  
FAY L. COBLENTZ
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reductive Cleavage ◽  
Steric Effects ◽  
Lithium Aluminum ◽  
Pyridine Solution
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