Intramolecular Reactions of Temporarily Silicon-Tethered Molecules

Fensterbank, Louis; Malacrìa, Max; Sieburth, Scott McN.

doi:10.1055/s-1997-1295

Cited by 176 publications

(61 citation statements)

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“…Preliminary studies examined the feasibility of this hypothesis for 1,4-stereocontrol (Scheme 2) through the examination of various substituents on silicon [9,10] and metal alkylidene catalysts, [11] as outlined in Table 1. Initial studies determined that the steric nature of the substituents on the silicon tether were indeed crucial in terms of silaketal construction, overall efficiency, and the level of diastereoselection, in which the diisopropylsilane proved optimal (Table 1; entry 3 versus 1 and 2).…”

mentioning

confidence: 99%

Diastereoselective Temporary Silicon‐Tethered Ring‐Closing‐Metathesis Reactions with Prochiral Alcohols: A New Approach to Long‐Range Asymmetric Induction

2003

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The ability to control stereochemistry in substrates where the reactive elements are distal represents a fundamentally important area of investigation that is commonly referred to as long-range asymmetric induction. [1,2] Although there are numerous examples of this phenomenon, a significant limitation with this type of process is the ability to predict the manner in which the chiral group attains proximity to the reactive site in order to translate stereochemical information. The inherent challenge associated with this requirement provided the incentive for the development of a new process where the elements of stereocontrol could be conserved in a predictable manner.[1, 2] Herein, we describe a new approach to long-range asymmetric induction using the diastereoselective temporary silicon-tethered (TST) ring-closing-metathesis (RCM) reaction of mixed bisalkoxy silanes 1, derived from an allylic and prochiral alcohol, for the construction of cis-1,4-silaketals 2 (Scheme 1; n = 0). This methodology was also extended to higher homologues (where n = 1-4), which resulted in the formation of the opposite trans diastereoisomer.

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confidence: 99%

Diastereoselective Temporary Silicon‐Tethered Ring‐Closing‐Metathesis Reactions with Prochiral Alcohols: A New Approach to Long‐Range Asymmetric Induction

2003

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“…The tethering of the dienophile to the diene moiety often facilitates Diels-Alder reactions and ensures the stereochemical outcome of the cycloaddition [56][57][58][59]. However, in our hands, linking quinone (S)-2 with allylic alcohol 16, either as a carbonate (cf.…”

Section: Other Dienes Studiedmentioning

confidence: 91%

Diels-Alder Reactions of 12-Hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione

et al. 2013

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12-Hydroxy-9(10→20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione (quinone 2) served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating) or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.

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“…Dies könnte der Reaktion nicht nur entropisch von Vorteil sein, sondern auch zu höheren Chemo-, Regio-und Stereoselektivitäten führen. Temporäre Siliciumbrücken haben sich in unzähligen Anwendungen als abspaltbare Linker bewährt, [55] und der vorliegende Fall ist ein weiteres lehrreiches Beispiel. [56,57] Wie in Schema 6 gezeigt, konnte das gemischte Dialkoxysilan einfach hergestellt werden, indem man den Allylalkohol 17 mit einem Überschuss an Diisopropyldichlorsilan zum entsprechenden Monoalkoxychlorsilan umsetzte, anschließend den Überschuss des Silylierungsmittels entfernte und den zweiten Allylalkohol 18 zugab.…”

Section: Die Alken-ringschlussmetatheseunclassified

Metathesereaktionen in der Totalsynthese

2005

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Mit Ausnahme der palladiumkatalysierten Kreuzkupplungsreaktionen hatte im vergangenen Vierteljahrhundert keine Reaktionsklasse einen derart weitreichenden Einfluss auf die Kohlenstoff‐Kohlenstoff‐Verknüpfung und die Totalsynthese wie die Metathesereaktionen von Olefinen, Eninen, und Alkinen. In diesem Aufsatz präsentieren wir Glanzlichter aus einer Reihe ausgewählter Totalsynthesen, in denen diese eleganten und effizienten Reaktionen entscheidend zum Erfolg beigetragen haben. Schon an ihrer kurzen, aber beeindruckenden Geschichte kann man ablesen, dass die Bedeutung dieser Reaktionen für die chemische Synthese weiter zunehmen wird.

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Intramolecular Reactions of Temporarily Silicon-Tethered Molecules

Cited by 176 publications

References 0 publications

Diastereoselective Temporary Silicon‐Tethered Ring‐Closing‐Metathesis Reactions with Prochiral Alcohols: A New Approach to Long‐Range Asymmetric Induction

Diastereoselective Temporary Silicon‐Tethered Ring‐Closing‐Metathesis Reactions with Prochiral Alcohols: A New Approach to Long‐Range Asymmetric Induction

Diels-Alder Reactions of 12-Hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione

Metathesereaktionen in der Totalsynthese

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