Synthesis of 2-Cyanomethyl Indane Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions of Alkyl Nitriles

Perez, Alma R.; Bornowski, Evan C.; Chen, Lei; Wolfe, John P.

doi:10.1021/acs.orglett.3c00571

Cited by 3 publications

(3 citation statements)

References 18 publications

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“…Following the seminal contributions from the Stahl group and our group, several famous research teams have substantially contributed to this developing field through innovative approaches and deep mechanistic insights . Although nonstereoselective Wacker-type functionalizations with C–H nucleophiles have been successfully implemented, research on their asymmetric versions remains limited (Scheme B) . In 2016, the Engle group reported a creative regioselective Wacker-type hydrocarbofunctionalization of internal alkenes with diverse C–H nucleophiles using a removable directing group strategy .…”

Section: Introductionmentioning

confidence: 99%

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Zhu,

Han,

Yang

et al. 2024

J. Am. Chem. Soc.

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The Wacker and Wacker-type reactions are some of the most fundamental and powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved in asymmetric oxy/aza-Wacker-type reactions; however, asymmetric Wacker-type dicarbofunctionalization remains underdeveloped, especially for the concurrent construction of two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio-and diastereodivergent Wacker-type dicarbofunctionalization of alkene-tethered aryl triflates with imino esters. A series of 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized in moderate to excellent yields and with good to excellent diastereo-and enantioselectivities (up to >20:1 dr and >99% ee). Density functional theory calculations revealed that the origin of diastereoselectivity in this Pd/Cu synergistic catalytic system is jointly determined by both the intermolecular anti-carbopalladation of alkenes and the reductive elimination processes, in accordance with the Curtin−Hammett principle.

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Section: Introductionmentioning

confidence: 99%

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Zhu,

Han,

Yang

et al. 2024

J. Am. Chem. Soc.

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“…Biindenes that lack carbonyl functionality on the indene ring are relatively rare and have most commonly been prepared via carbocation intermediates or from reductive deoxygenation of the corresponding indanones . However, although relatively few biindene derivatives are known, some of these derivatives have interesting and potentially useful biological activities, including smooth muscle relaxing activity, mast cell stabilizing activity, or anti-inflammatory activity .…”

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confidence: 99%

“…We recently described a new Pd-catalyzed cross-coupling (alkene difunctionalization) reaction between nitrile nucleophiles and 2-allylphenyl triflate derivatives or related alkenyl triflates. − During the course of these studies, we found that transformations of relatively bulky α-branched nitriles were generally effective (Scheme , eq 1). However, yields decreased as the size of the alkyl chain decreased, with competing direct α-arylation of the nitrile becoming increasingly problematic.…”

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confidence: 99%

Synthesis of Biindene Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions

Perez,

Hanks,

Bornowski

et al. 2024

Org. Lett.

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The palladium-catalyzed cross-coupling of 2-allylphenyl triflate and related electrophiles with substituted indenes affords biindene derivatives in moderate to good yields with high selectivity for thermodynamically preferred alkene isomers. The transformations involve alkene nucleopalladation with indenyl anions, and we also demonstrate that 2-allylphenyl triflates can be transformed to indenes under similar conditions. The scope of this transformation, along with the mechanism of formation of both indene and biindene products, is described.

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Ionic Liquid Immobilized Pd Nanocatalysts for Chemoselective Reduction of Aliphatic/Aromatic Nitro Compounds

Prakash

Jangir

Srivastava

2023

LOC

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Introduction: In this work, we have successfully synthesized four types of ionic liquid-mediated Pd nanocatalysts and performed the physiochemical analysis of the developed Pd-based nanocatalysts using a transmission electron microscope (TEM), X-Ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), and atomic absorption spectroscopy (AAS) analysis. Method: The well-dispersed and fine Pd nanoparticles were recorded in the ILPdNPs-4 catalytic system. We used this catalytic system to reduce a series of aliphatic and aromatic compounds with nitro groups and developed various biologically active amine molecules. In the continuation of the same, we also reduced nitrolactone, which is considered one of the important starting materials for the synthesis of renin inhibitor aliskiren (Tekturna®, and worldwide as Rasilez®). Result: We also completed the catalyst stability test and recycled the ILPdNPs-4 catalytic system for up to eight runs. Conclusion: No sign of metal leaching, Pd black formation, and agglomeration was recorded during recycling runs.

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Synthesis of 2-Cyanomethyl Indane Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions of Alkyl Nitriles

Cited by 3 publications

References 18 publications

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Synthesis of Biindene Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions

Ionic Liquid Immobilized Pd Nanocatalysts for Chemoselective Reduction of Aliphatic/Aromatic Nitro Compounds

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