Catalytic Asymmetric Carbohydroxylation of Alkenes by a Tandem Diboration/Suzuki Cross-Coupling/Oxidation Reaction

Miller, Steven P.; Morgan, Jeremy B.; Nepveux, Felix J.; Morken, James P.

doi:10.1021/ol036219a

Cited by 124 publications

(45 citation statements)

References 21 publications

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“…Thus, reactive, tricoordinate, C(sp 2 )-hybridized organoboron reagents that succumb to decomposition pathways such as oxidation and protodeboronation during traditional Pd-mediated coupling conditions remained intact using the orthogonal photoredox/Ni cross-coupling protocols (Scheme 9). 32 …”

Section: Photoredox/nickel Dual Catalysismentioning

confidence: 99%

Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development

et al. 2017

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Photoredox catalysis has experienced a revitalized interest from the synthesis community during the past decade. For example, photoredox/Ni dual catalysis protocols have been developed to overcome several inherent limitations of palladium-catalyzed cross-couplings by invoking a single-electron transmetalation pathway. This Perspective highlights advances made by our laboratory since the inception of the photoredox/Ni cross-coupling of benzyltrifluoroborates with aryl bromides. In addition to broadening the scope of trifluoroborate coupling partners, research using readily oxidized hypervalent silicates as radical precursors that demonstrate functional group compatibility is highlighted. The pursuit of electrophilic coupling partners beyond (hetero)aryl bromides has also led to the incorporation of several new classes of C(sp2)-hybridized substrates into light-mediated cross-coupling. Advances to expand the radical toolbox by utilizing feedstock chemicals (e.g., aldehydes) to access radicals that were previously inaccessible from trifluoroborates and silicates are also emphasized. Additionally, several organic photocatalysts have been investigated as replacements for their expensive iridium- and ruthenium-based counterparts. Lastly, the net C–H functionalization of the radical partner in an effort to improve atom economy is presented. An underlying theme in all of these studies is the value of generating radicals in a catalytic manner, rather than stoichiometrically.

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Section: Photoredox/nickel Dual Catalysismentioning

confidence: 99%

Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development

et al. 2017

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“…A far greater range of new molecular building blocks would arise from terminal alkenes if 1,2-bis(pinacol boronates) would directly participate in efficient cross-coupling. While related cross-couplings with bis(catechol boronates) are known, 8 conversion of terminal alkenes to enantiomerically enriched 1,2-bis(catechol boronates) is generally not enantioselective. Therefore, a strategy for terminal alkene manipulation based on selective diboration reactions requires successfully engaging alkyl pinacol boronates as nucleophilic partners in Suzuki-Miyaura cross coupling.…”

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confidence: 99%

Asymmetric synthesis from terminal alkenes by cascades of diboration and cross-coupling

Mlynarski

Schuster

Morken

2013

Nature

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248

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Amongst prospective starting materials for organic synthesis, terminal (monosubstituted) alkenes are ideal. In the form of α-olefins, they are manufactured on enormous scale and they are the core product features from many organic chemical reactions. While their latent reactivity can easily enable hydrocarbon chain extension, alkenes also have the attractive feature of being stable in the presence of many acids, bases, oxidants and reductants. In spite of these impressive attributes, relatively few catalytic enantioselective transformations have been developed that transform aliphatic α-olefins in >90% ee and, with the exception of site-controlled isotactic polymerization of α-olefins,1 none of these processes result in chain-extending C-C bond formation to the terminal carbon.2, 3, 4, 5, 6 Herein, we describe a strategy that directly addresses this gap in synthetic methodology and present a single-flask catalytic enantioselective conversion of terminal alkenes into a range of chiral products. These reactions are enabled by an unusual neighboring group participation effect that accelerates Pd-catalyzed cross-coupling of 1,2-bis(boronates) relative to nonfunctionalized alkyl boronate analogs. In tandem with enantioselective diboration, this reactivity feature connects abundant alkene starting materials to a diverse array of chiral products. Importantly with respect to synthesis utility, the tandem diboration/cross-coupling reaction (DCC reaction) generally provides products in high yield and high selectivity (>95:5 enantiomer ratio), employs low loadings (1–2 mol %) of commercially available catalysts and reagents, it offers an expansive substrate scope, and can address a broad range of alcohol and amine synthesis targets, many of which cannot be easily addressed with current technology.

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“…[128,129] Morken und Mitarbeiter berichteten außerdem über die ersten ligandkontrollierten asymmetrischen Platin(0)-katalysierten Diborierungsreaktionen. In einer späteren Untersuchung derselben Gruppe wurde nachgewiesen, dass eine Erhçhung des sterischen Anspruchs in Nachbarschaft zum terminalen Alken (im Allgemeinen ein quartäres Stereozentrum) eine Diborierung dieser Substrate mit synthetisch nützlichen Enantioselektivitäten erlaubt, wodurch Moleküle entstehen, die sowohl eine primäre als auch eine sekundäre Alykboronsäureesterfunktion mit unterschiedlichen Reaktivitätsprofilen enthalten.…”

Section: Angewandte Chemieunclassified

Asymmetrische Synthese sekundärer und tertiärer Boronsäureester

Collins¹,

Wilson²,

Myers³

et al. 2017

Angewandte Chemie

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Nicht‐racemische chirale Boronsäureester sind äußerst wertvolle Bausteine in der modernen organischen Synthese. Ihre stereospezifische Umwandlung in diverse funktionelle Gruppen – von Aminen und Halogeniden bis hin zu Arenen und Alkinen – zusammen mit ihrer Luft‐ und Feuchtigkeitsstabilität haben sie als wichtige Zielverbindungen für die asymmetrische Synthese etabliert. Die Bemühungen im Hinblick auf eine stereoselektive Synthese sekundärer und tertiärer Alkylboronsäureester erstrecken sich mittlerweise auf mehr als fünf Dekaden und werden von einer Fülle an Reaktivitätsplattformen untermauert, die sich der einzigartigen und mannigfaltigen Reaktivität von Bor bedienen. Dieser Aufsatz fasst Strategien für die asymmetrische Synthese von Alkylboronsäureestern zusammen, beginnend mit den wegweisenden Hydroborierungsmethoden von H. C. Brown bis hin zu den modernsten Herangehensweisen.

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Catalytic Asymmetric Carbohydroxylation of Alkenes by a Tandem Diboration/Suzuki Cross-Coupling/Oxidation Reaction

Cited by 124 publications

References 21 publications

Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development

Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development

Asymmetric synthesis from terminal alkenes by cascades of diboration and cross-coupling

Asymmetrische Synthese sekundärer und tertiärer Boronsäureester

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