Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

Zhang, Yun; Chen, Gong; Zhao, Dongbing

doi:10.1039/c9sc02182e

Cited by 74 publications

(34 citation statements)

References 67 publications

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“…Mechanistic studies. In analogy to earlier work [34][35][36][37][38][39][40][41][42][43][44][45][46][47] , we surmised that the reaction may proceed by the general mechanism depicted in Fig. 2c, involving a sequence of alkene coordination, nucleopalladation, intramolecular oxidative addition, and reductive elimination.…”

Section: Scope Of Alkenessupporting

confidence: 66%

“…During the past 5 years, our laboratories have developed a variety of transition-metal-catalyzed, three-component directed alkene 1,2-difunctionalization reactions facilitated by the 8aminoquinoline (AQ) auxiliary, a strongly coordinating bidentate directing group. Using this strategy we and others have reported examples of hydrofunctionalization [21][22][23][24][25][26][27][28][29][30][31][32][33] , dicarbofunctionalization [34][35][36][37][38][39] , carboamination 40,41 , and carbo-/aminoboration [42][43][44][45] , among other transformations 46,47 (Fig. 1c).…”

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confidence: 94%

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Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

Kevlishvili

Bedekar

et al. 2020

Nat Commun

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Abstract2,3-Dihydrobenzofurans and indolines are common substructures in medicines and natural products. Herein, we describe a method that enables direct access to these core structures from non-conjugated alkenyl amides and ortho-iodoanilines/phenols. Under palladium(II) catalysis this [3 + 2] heteroannulation proceeds in an anti-selective fashion and tolerates a wide variety of functional groups. N-Acetyl, -tosyl, and -alkyl substituted ortho-iodoanilines, as well as free –NH2 variants, are all effective. Preliminary results with carbon-based coupling partners also demonstrate the viability of forming indane core structures using this approach. Experimental and computational studies on reactions with phenols support a mechanism involving turnover-limiting, endergonic directed oxypalladation, followed by intramolecular oxidative addition and reductive elimination.

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Section: Scope Of Alkenessupporting

confidence: 66%

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confidence: 94%

Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

Kevlishvili

Bedekar

et al. 2020

Nat Commun

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“…Though useful in its own right, this method is limited in terms of the carbogenic groups that can be introduced (indole‐type nucleophiles) and the alkene scope (terminal and 1,2‐disubstituted alkenes). We hypothesized that these issues could be overcome by developing a catalytic system that instead initiates via Heck‐type 1,2‐migratory insertion . Based on this idea, herein we describe a Heck‐type directed 1,2‐carboboration that proceeds via a Pd 0 /Pd II redox manifold (Scheme D).…”

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

Liu

et al. 2019

Angewandte Chemie

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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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“…Achieving regioselectivity in these cases has therefore relied on chelation control through the use of a directing group. [21][22][23][24] Unfortunately, amines are generally regarded as poor directing groups for this process, and have required conversion into static amide and carbamate-type directing groups, [25][26][27][28][29][30][31] which negatively impacts both step and atom economy of these transformations. Inspired by the recent popularity of transient directing groups in the field of C-H activation, [32][33][34] we wondered if the proposed oxidative arylation of allylamines could be realized using a transient directing group suitable for amines.…”

mentioning

confidence: 99%

CO2 As A Transient Directing Group for the Oxidative Heck Coupling of Free Allylamines With Aryl Iodides

Landge¹,

Maxwell²,

Chand-Thakuri³

et al. 2020

Preprint

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Oxidative Heck couplings are a powerful method for elaborating alkene feedstocks. While selective functionalization of terminal olefins has been achieved by catalyst design, selective functionalization of internal olefins has generally required use of directing groups except in the case of Michael acceptors. Allylamine substrates have typically required protection to be suitable for these reactions, decreasing the step and atom economy of these procedures. Herein we demonstrate that the addition of CO2 (dry ice) as a transient directing group allows for the stereospecific arylation of both secondary and primary allylamines in the presence of a PdII catalyst. Notably, the product 3,3’-diarylallylamine motif is prevalent in a variety of biologically-relevant structures, and this method represents the most straightforward synthesis of these targets to date. 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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Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids

Abstract: Transmetalation-initiated three-component vicinal-diarylation of alkenes.

Cited by 74 publications

References 67 publications

Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

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

CO2 As A Transient Directing Group for the Oxidative Heck Coupling of Free Allylamines With Aryl Iodides

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