Chromium-Catalyzed Pinacol-Type Cross-Coupling : Studies on Stereoselectivity

Groth, Ulrich; Jung, Marc; Vogel, Till

Chromium-Catalyzed Pinacol-Type Cross-Coupling : Studies on Stereoselectivity

Files

Groth_Chromium_Catalyzed.pdf(269.48 KB)

Date

2005

Authors

Groth, Ulrich

Jung, Marc

Vogel, Till

Publication type

Journal article

Published in

Chemistry - A European Journal ; 11 (2005), 10. - pp. 3127-3135. - ISSN 0947-6539. - eISSN 1521-3765

Abstract

A chromium-catalyzed pinacol-type cross-coupling reaction between α,β-unsaturated carbonyl compounds and aldehydes is reported. Even sterically demanding substrates could be coupled to afford the corresponding pinacols in good yields. Systematic studies concerning the origin of the diastereoselectivities led to the proposal of a mechanism for this synthetically useful reaction. Acroleins with α-branched alkyl side chains were coupled to give the corresponding syn pinacols, while on the other hand, acroleins with less bulky substituents furnished the anti derivatives. The effects of both the substrates and the reagents on the diastereo- and enantioselectivities were investigated. An unexpected catalytic formation of cyclopropanols was found.

Summary in another language

Eine Chrom-katalysierte Pinakol Kreuz-Kupplung zwischen α,β-ungesättigten Carbonylverbindungen und Aldehyden wird vorgestellt. Sogar sterisch anspruchsvolle Substrate können in hohen Ausbeuten zu den entsprechenden Pinakolen umgesetzt werden. Durch systematische Untersuchungen hinsichtlich der Diastereoselektivität konnte ein Mechanismus für diese synthetisch wertvolle Reaktion postuliert werden. Acroleine die in α-Position verzweigte Alkylketten tragen, ergaben bevorzugt syn-Pinakole, wohingegen sterisch weniger anspruchsvolle Substituenten bevorzugt anti-Derivate lieferten. Es wurden Substrat- und Reagenzeffekte im Hinblick auf die erhaltenen Diastereo- und Enantioselektivitäten untersucht. Dabei wurde überraschenderweise eine diastereoselektive Bildung von Cyclopropanolen gefunden.

Subject (DDC)

540 Chemistry

Keywords

chromium,cross- coupling,diastereoselectivity,homogeneous catalysis,pinacols

Cite This

ISO 690

GROTH, Ulrich, Marc JUNG, Till VOGEL, 2005. Chromium-Catalyzed Pinacol-Type Cross-Coupling : Studies on Stereoselectivity. In: Chemistry - A European Journal. 11(10), pp. 3127-3135. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.200400304

BibTex

@article{Groth2005Chrom-10057,
  year={2005},
  doi={10.1002/chem.200400304},
  title={Chromium-Catalyzed Pinacol-Type Cross-Coupling : Studies on Stereoselectivity},
  number={10},
  volume={11},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={3127--3135},
  author={Groth, Ulrich and Jung, Marc and Vogel, Till}
}

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