Intermolecular Heck Coupling with Hindered Alkenes Directed by Potassium Carboxylates

Huffman, Tucker R.; Wu, Yebin; Emmerich, Alexis; Shenvi, Ryan A.

doi:10.1002/anie.201813233

Cited by 33 publications

(20 citation statements)

References 57 publications

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“…To complement these approaches,w er easoned that as ubstrate-directed strategy involving palladium catalysis could enhance reactivity with hindered substrates (e.g., tetrasubstituted alkenes [8] )and provide ameans of controlling regioselectivity in amanner that is independent of the alkene substitution pattern. Previously,o ur lab [9] and others [10] have developed at oolkit of hydro-and difunctionalization reactions of alkenyl carbonyl compounds bearing the 8-aminoquinoline [11] (AQ) directing group.A sp art of this effort, we described an anti-selective 1,2-carboboration of alkenyl carbonyl compounds that initiates via Wacker-type carbopalladation (Scheme 1C).…”

Section: Introductionmentioning

confidence: 99%

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

et al. 2019

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We report the development of palladium(0)‐catalyzed syn‐selective 1,2‐carboboration and ‐silylation reactions of alkenes containing cleavable directing groups. With B2pin2 or PhMe2Si‐Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono‐, di‐, tri‐ and tetrasubstituted alkenes are compatible in these transformations. We further describe a directed dearomative 1,2‐carboboration of electron‐rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck‐type alkene 1,2‐difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio‐ and stereocontrol.

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Section: Introductionmentioning

confidence: 99%

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

et al. 2019

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“… 5 − 9 As a result, there are numerous approaches to their synthesis. 10 − 13 A powerful approach for the arylation of olefins is the Mizoroki–Heck (MH) reaction, 14 , 15 though internal olefin substrates often require directing groups to achieve reasonable regioselectivity. 16 − 19 In the case of allylamine substrates, protection of the amine has been required ( Scheme 1 a) to achieve these reactions, 20 − 24 and the reactions are limited to a single arylation except in a few circumstances ( Scheme 1 b).…”

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confidence: 99%

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Landge

Maxwell

Chand-Thakuri

et al. 2020

JACS Au

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Palladium-catalyzed organometallic transformations of free amines are often unsuccessful due to side reactions, such as oxidation, that can occur. However, the ability to furnish the free amine products from these reactions is important for improving the utility and sustainability of these processes, especially for accessing their potential as medicinal and agrochemical agents. Notably, the 3,3-diarylallylamine motif is prevalent in a variety of biologically relevant structures, yet there are few catalytic approaches to their synthesis, and none involving the free amine. Herein, we describe a simple protocol for the arylation of cinnamylamines and the diarylation of terminal allylamines to generate a diverse group of 3,3-diarylallylamine products using a Pd II precatalyst. Key features of the method are the ability to access relatively mild conditions that facilitate a broad substrate scope as well as direct diarylation of terminal allylamine substrates. In addition, several complex and therapeutically relevant molecules are included to demonstrate the utility of the transformation.

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“…A plausible catalytic cycle for this nickel‐catalyzed 1,2‐diarylation of alkenyl carboxylates is shown in Scheme . Under the basic conditions, the substrate is expected to exist primarily as the corresponding sodium carboxylate salt, which could potentially coordinate to the nickel catalyst in either an l ‐type or X‐type fashion, and the coordination mode could be dynamic throughout the catalytic cycle. For simplicity the L‐type binding mode is shown in Scheme in analogy to our earlier amide‐directed system .…”

Section: Methodsmentioning

confidence: 99%

Nickel‐Catalyzed 1,2‐Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3‐Trifunctionalized Building Blocks

et al. 2019

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A nickel‐catalyzed conjunctive cross‐coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2‐diarylated and 1,2‐arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3‐trifunctionalized building blocks using two‐electron and one‐electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2‐diarylation of an alkene directed by a native carboxylate group.

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Intermolecular Heck Coupling with Hindered Alkenes Directed by Potassium Carboxylates

Cited by 33 publications

References 57 publications

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Nickel‐Catalyzed 1,2‐Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3‐Trifunctionalized Building Blocks

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