Stereocontrolled synthesis of Z-dienes via an unexpected pericyclic cascade rearrangement of 5-amino-2,4-pentadienals

Journal of the American Chemical Society

Volumn 130, Issue 24, 2008, Pages 7560-7561

  Steinhardt, Sarah E ^a   Silverston, Joel S ^a   Vanderwal, Christopher D ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

5 AMINO 2,4 PENTADIENAL DERIVATIVE; ALKADIENE; POLYENE; PYRIDINIUM DERIVATIVE;

AMINOLYSIS; ARTICLE; CHEMICAL REACTION; CYCLOADDITION; REACTION ANALYSIS; RING OPENING; STEREOCHEMISTRY; SYNTHESIS;

ALDEHYDES; NITROBENZENES; POLYENES; STEREOISOMERISM;

EID: 45249091848     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8028125     Document Type: Article

References (31)

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20. At this stage, we have no further experimental support for this hypothesis, though it does fit the observed reactivity. The formation of 15 can also be viewed as a carbonyl addition reaction by the nitrogen atom in 14 (non-zwitterionic resonance structure) to generate the cyclic zwitterion.
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22. A thermal rearrangement of an unusual tetrachlorinated doubly vinylogous thioester to the corresponding α,β,γ,δ-unsaturated thioester was proposed to proceed viapyran intermediates and a [1,5]-C1 shift: Roedig, A.; Göpfert, H. Chem. Ber. 1981, 114, 3625-3633.
23. On the basis of literature precedent and our own exploratory experiments, Zincke aldehydes with any substitution at C1 or C5 (derived from pyridine C2 and C6) are not accessible from the pyridine ring-opening process. Due to the regioselectivity of the ring-opening aminolysis/iminium hydrolysis process, monosubstitution at C4 is also not possible using this route. Studies to access substituted Zincke aldehydes by other means are underway.
24. Presumably, the Z to E isomerization is not purely thermal but is instigated by an impurity in the reaction medium. To date, we have been unable to fully suppress the isomerization. Fortunately, those products that are most difficult to access with high Z-selectivity (7 and 17) are those that might be readily obtained by alkyne semi-hydrogenation.
25. We have confirmed the alkene stereochemistry of our products spectroscopically and by comparison to known compounds. See the Supporting Information for details.
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31. (c) For the structure of this catalyst, please see the Supporting Information.