Bicyclic cyclopentenones via the combination of an iridium- catalyzed allylic substitution with a diastereoselective intramolecular Pauson–Khand reaction

Andreas Farwick; Jens Engelhart; Olena Tverskoy; Carolin Welter; Quendolin Umlauf; Frank Rominger; William Kerr; Gunter Helmchen

doi:10.1002/adsc.201000706

Bicyclic cyclopentenones via the combination of an iridium- catalyzed allylic substitution with a diastereoselective intramolecular Pauson–Khand reaction

Andreas Farwick, Jens Engelhart, Olena Tverskoy, Carolin Welter, Quendolin Umlauf, Frank Rominger, William Kerr, Gunter Helmchen

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

32 Citations (Scopus)

Abstract

Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an Ir-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found to be crucially dependent on the unit connecting the propargylic and the olefinic units of the precursor. Very high degrees of diastereoselection were obtained with an NBoc unit as connector. This methodology has been illustrated by application within an enantioselective formal total synthesis of (-)-α-kainic acid.

Original language	English
Pages (from-to)	349-370
Number of pages	22
Journal	Advanced Synthesis and Catalysis
Volume	353
Issue number	2-3
DOIs	https://doi.org/10.1002/adsc.201000706
Publication status	Published - 11 Feb 2011

Keywords

alkyne ligands
enantioselective total synthesis
asymmetric total synthesis
Pauson-Khand reaction
alkaloids
(-)
Japanese hop ether
iridium
allylic substitution
efficient chiral auxiliary
amine N-oxide
formal total-synthesis
asymmetric catalysis

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10.1002/adsc.201000706

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title = "Bicyclic cyclopentenones via the combination of an iridium- catalyzed allylic substitution with a diastereoselective intramolecular Pauson–Khand reaction",

abstract = "Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an Ir-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found to be crucially dependent on the unit connecting the propargylic and the olefinic units of the precursor. Very high degrees of diastereoselection were obtained with an NBoc unit as connector. This methodology has been illustrated by application within an enantioselective formal total synthesis of (-)-α-kainic acid. ",

keywords = "alkyne ligands, enantioselective total synthesis, asymmetric total synthesis, Pauson-Khand reaction, alkaloids, (-), Japanese hop ether, iridium, allylic substitution, efficient chiral auxiliary, amine N-oxide, formal total-synthesis, asymmetric catalysis",

author = "Andreas Farwick and Jens Engelhart and Olena Tverskoy and Carolin Welter and Quendolin Umlauf and Frank Rominger and William Kerr and Gunter Helmchen",

year = "2011",

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day = "11",

doi = "10.1002/adsc.201000706",

language = "English",

volume = "353",

pages = "349--370",

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T1 - Bicyclic cyclopentenones via the combination of an iridium- catalyzed allylic substitution with a diastereoselective intramolecular Pauson–Khand reaction

AU - Farwick, Andreas

AU - Engelhart, Jens

AU - Tverskoy, Olena

AU - Welter, Carolin

AU - Umlauf, Quendolin

AU - Rominger, Frank

AU - Kerr, William

AU - Helmchen, Gunter

PY - 2011/2/11

Y1 - 2011/2/11

N2 - Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an Ir-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found to be crucially dependent on the unit connecting the propargylic and the olefinic units of the precursor. Very high degrees of diastereoselection were obtained with an NBoc unit as connector. This methodology has been illustrated by application within an enantioselective formal total synthesis of (-)-α-kainic acid.

AB - Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an Ir-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found to be crucially dependent on the unit connecting the propargylic and the olefinic units of the precursor. Very high degrees of diastereoselection were obtained with an NBoc unit as connector. This methodology has been illustrated by application within an enantioselective formal total synthesis of (-)-α-kainic acid.

KW - alkyne ligands

KW - enantioselective total synthesis

KW - asymmetric total synthesis

KW - Pauson-Khand reaction

KW - alkaloids

KW - (-)

KW - Japanese hop ether

KW - iridium

KW - allylic substitution

KW - efficient chiral auxiliary

KW - amine N-oxide

KW - formal total-synthesis

KW - asymmetric catalysis

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U2 - 10.1002/adsc.201000706

DO - 10.1002/adsc.201000706

M3 - Article

SN - 1615-4150

VL - 353

SP - 349

EP - 370

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

IS - 2-3

ER -

Bicyclic cyclopentenones via the combination of an iridium- catalyzed allylic substitution with a diastereoselective intramolecular Pauson–Khand reaction

Abstract

Keywords

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