Total Synthesis of (−)-Cylindrocyclophanes A and F Exploiting the Reversible Nature of the Olefin Cross Metathesis Reaction

Efficient total syntheses of the C 2-symmetric (−)-cylindrocyclophanes A and F (1a and 1f) have been achieved. The initial strategy featured the use of a common advanced intermediate to assemble in stepwise fashion the required macrocycle of 1f, exploiting in turn a Myers reductive coupling followed...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2001-06, Vol.123 (25), p.5925-5937
Main Authors: Smith, Amos B, Adams, Christopher M, Kozmin, Sergey A, Paone, Daniel V
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Chemistry, Organic - methods
Dimerization
Indicators and Reagents
Mass Spectrometry
Molecular Conformation
Molecular Structure
Polycyclic Aromatic Hydrocarbons
Stereoisomerism
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Summary:Efficient total syntheses of the C 2-symmetric (−)-cylindrocyclophanes A and F (1a and 1f) have been achieved. The initial strategy featured the use of a common advanced intermediate to assemble in stepwise fashion the required macrocycle of 1f, exploiting in turn a Myers reductive coupling followed by ring-closing metathesis. In a second-generation strategy, a remarkable cross olefin metathesis dimerization cascade was discovered and exploited to assemble the requisite [7,7]-paracyclophane macrocycles of both 1a and 1f from dienyl monomers. The successful syntheses also featured the effective use of the Danheiser annulation to construct substrates for both the Myers reductive coupling and the metathesis dimerizations strategies. Finally, the Kowalski two-step chain homologation of esters to siloxyalkynes proved superior over the original one-step protocol.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0106164