Hydride Reductions of 1-Phenyl-1-nonen-3 -one: Mass Spectrometry of 1-Phenyl-1-nonen-3-ols and Relative Stereochemistry of the Diastereoisomeric 4-Dimethylaminomethyl-1-Phenyl-1-nonen-3-ols

1974 ◽  
Vol 52 (13) ◽  
pp. 2522-2530 ◽  
Author(s):  
Wesley Gordon Taylor ◽  
Jonathan Richard Dimmock
Keyword(s):  
Aluminum Hydride ◽  
Addition Product ◽  
Mannich Bases ◽  
Allylic Alcohol ◽  
Lithium Aluminum ◽  
Allylic Alcohols ◽  
Carbonyl Carbon Atom ◽  
Methyl Radical ◽  
Mass Spectral ◽  
Relative Stereochemistry

The metal hydride reduction products of some styryl ketones and dimethylaminomethyl Mannich bases have been investigated. Sodium borohydride selectively attacked the carbonyl carbon atom to give the desired allylic alcohols. Reduction of 1-phenyl-1-nonen-3-one with lithium aluminum hydride gave 1-phenyl-3-nonanol which represents the conjugate addition product. Fragmentations of 1-phenyl-1-nonen-3-ol were compared to the modes of mass spectral breakdown of 4-phenyl-3-buten-2-ol, an allylic alcohol which is known to behave like a saturated ketone on electron bombardment. Peaks corresponding to the McLafferty ion and the loss of a methyl radical from this rearrangement product were observed. Certain Mannich bases were reduced to diastereoisomeric allylic amino alcohols. The separation, 1H n.m.r. spectroscopy, and relative stereochemistry of the diastereoisomers are discussed.

Lithium Aluminum Hydride Reductive Rearrangement of Allylic Acetals to Vinyl Ethers: A Synthesis of 3-Deoxy Glycals

1975 ◽  
Vol 53 (13) ◽  
pp. 2005-2016 ◽  
Author(s):  
Bert Fraser-Reid ◽  
Steve Y-K. Tam ◽  
Bruno Radatus
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Hydroxyl Group ◽  
Lithium Aluminum ◽  
Allylic Alcohols ◽  
Vinyl Ethers ◽  
Hydride Ion ◽  
Lithium Aluminium ◽  
Leaving Group ◽  
Ethereal Oxygen

Carbohydrate allylic acetals (hex-2-enopyranosides) are reductively rearranged to vinyl ethers (3-deoxy glycals) by treatment with lithium aluminium hydride in refluxing ethereal solvents. Under similar conditions, some allylic alcohols are also reductively rearranged to olefins, although the reaction appears to be confined to carbohydrate substrates since the reaction fails with typical carbocyclic allylic alcohols.The results are rationalized by postulating the intermediacy of an oxygen–alane complex, this being formed more readily in the case of an hydroxyl (or ester) rather than an ethereal oxygen. An axial oxygen permits easier achievement of the reactive transition state than an equatorial oxygen. The complex normally leads to an SN2' reductive rearrangement in which the entering hydride and departing oxygen are syn-related. Alternatively, and particularly when the double bond is flanked by an hydroxyl group at one allylic position and a leaving group at the other, an abnormal SN2′ process may occur so that the hydride ion is delivered vicinal and cis to the hydroxyl group, with ejection of the leaving group. The process is at all times stereospecific but not always regiospecific.

scholarly journals Spirolucidine, a new Lycopodium alkaloid

1984 ◽  
Vol 62 (2) ◽  
pp. 298-302 ◽  
Author(s):  
William A. Ayer ◽  
Leslie F. Ball ◽  
Lois M. Browne ◽  
Motoo Tori ◽  
Louis T. J. Delbaere ◽  
...  
Keyword(s):  
Spectroscopic Data ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
X Ray ◽  
Hydride Reduction ◽  
Crystallographic Study ◽  
Lycopodium Alkaloid ◽  
Relative Stereochemistry ◽  
New Type

The structure of spirolucidine, a new type of Lycopodium alkaloid related to the lucidines, has been determined. Chemical and spectroscopic data, together with biogenetic considerations, led to the correct constitution of spirolucidine. An X-ray crystallographic study of tetrahydrodeoxyspirolucidine, the lithium aluminum hydride reduction product of spirolucidine, confirmed the constitution and established the relative stereochemistry of the alkaloid.

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