Ein vielseitiges Bisallylbor‐Reagenz für die stereoselektive Synthese von chiralen Diolen

The ability of cyclooctatetraene oxide to undergo two sequential ring contraction events under mild conditions, using Brønsted acid catalysis, has been studied in detail. We have found that the selectivity can be controlled by the acidity of the catalyst and by the temperature, being able to obtain selectively either the cycloheptatriene carbaldehyde product, arising from a single ring-contraction event, or phenylacetaldehyde that is formed after a second ring contraction process. A complete mechanistic picture of the reaction and a rationale behind the influence of the catalyst is provided based on both experimental and computational data. Finally, this acid-catalyzed ring contraction has been coupled with an in situ enantioselective allylation reaction, delivering enantioenriched cycloheptatrienyl-substituted homoallylic alcohols when it is carried out in the presence of a chiral phosphoric acid catalyst. These homoallylic alcohols have also been converted into enantioenriched oxaborinanes through copper-catalyzed nucleophilic borylation/cyclization protocol.

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Switchable Brønsted Acid‐Catalyzed Ring Contraction of Cyclooctatetraene Oxide Towards the Enantioselective Synthesis of Cycloheptatrienyl‐Substituted Homoallylic Alcohols and Oxaborinanes

Fernández

Sendra

Salvadó

et al. 2023

Adv Synth Catal

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Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols

et al. 2021

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We report herein the development of stereodivergent syntheses of enantioenriched homoallylic alcohols using chiral nonracemic a-CH 2 Bpin-substituted crotylboronate.C hiral phosphoric acid (S)-A-catalyzed asymmetric allyl addition with the reagent gave Z-anti-homoallylic alcohols with excellent enantioselectivities and Z-selectivities.W hen the enantiomeric acid catalyst (R)-A was utilized,t he stereoselectivity was completely reversed and E-anti-homoallylic alcohols were obtained with high E-selectivities and excellent enantioselectivities.B ypairing the chirality of the boron reagent with the catalyst, two complementary stereoisomers of chiral homoallylic alcohols can be obtained selectively from the same boron reagent. DFT computational studies were conducted to probe the origins of the observed stereoselectivity.T hese reactions generate highly enantioenriched homoallylic alcohol products that are valuable for rapid construction of polyketide structural frameworks.

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Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols

et al. 2021

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Ein vielseitiges Bisallylbor‐Reagenz für die stereoselektive Synthese von chiralen Diolen

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 3 publications

References 52 publications

Switchable Brønsted Acid‐Catalyzed Ring Contraction of Cyclooctatetraene Oxide Towards the Enantioselective Synthesis of Cycloheptatrienyl‐Substituted Homoallylic Alcohols and Oxaborinanes

Switchable Brønsted Acid‐Catalyzed Ring Contraction of Cyclooctatetraene Oxide Towards the Enantioselective Synthesis of Cycloheptatrienyl‐Substituted Homoallylic Alcohols and Oxaborinanes

Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols

Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols

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