Palladium‐Catalyzed Asymmetric Reductive Heck Reaction of Aryl Halides

Yue, Guizhou; Lei, Kaining; Hirao, Hajime; Zhou, Jianrong

doi:10.1002/ange.201501712

Cited by 60 publications

(3 citation statements)

References 104 publications

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“…The alcohol was known to promote reversible ionization of arylpalladium halides in Heck reactions. [12] The ionization creates a vacant site, which is crucial for subsequent alkene insertion, palladium migration, and formation of cationic p-cycloallyl species (see Figure 1 c).…”

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confidence: 99%

Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

et al. 2020

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Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5‐aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines.

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Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

et al. 2020

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“…The hindered base N , N ‐diisopropylethylamine (DIPEA) showed poor selectivity, probably as a result of decreased coordination to the palladium center (Table 3, Entry 4), although this base has been used with excellent results in the reductive Heck reactions reported recently by Zhou et al22 The bicyclic base 1,4‐diazabicyclo[2.2.2]octane (DABCO) also showed poor selectivity, which we attributed to slow hydride transfer to the palladium atom (Table 3, Entry 3).…”

Section: Resultsmentioning

confidence: 99%

Palladium‐Catalyzed Suzuki–Miyaura, Heck and Hydroarylation Reactions on (–)‐Levoglucosenone and Application to the Synthesis of Chiral γ‐Butyrolactones

et al. 2015

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The chiral pool material (–)‐levoglucosenone (6,8‐dioxabicyclo[3.2.1]oct‐2‐en‐4‐one, LGO) has been substituted by using a series of Pd‐mediated cross‐coupling reactions. Iodination of LGO followed by Suzuki–Miyaura cross‐coupling reaction with boronic acids by employing the Buchwald ligand SPhos with Pd(OAc)2 afforded 3‐aryl derivatives in excellent yields. Selective Heck arylation reaction at the 2‐position was achieved with aryl iodides with K3PO4 as base and SPhos ligand with Pd(OAc)2 (1–5 mol‐%). A selective hydroarylation reaction (formal conjugate addition) was developed by using the same aryl iodides, benzyldiethylamine, Pd(OAc)2, and P(o‐tol)3. The products were converted, either directly or after alkene reduction, through a Baeyer–Villiger oxidation into chiral 3‐ and 4‐substituted 5‐(hydroxymethyl)dihydrofuran‐2(3H)‐ones.

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“…Since then, synthesis of diverse spiro compounds has been widely developed via the palladium‐catalyzed Heck reaction protocol [38] . Meanwhile, the palladium‐catalyzed reductive Heck reaction of olefins with aryl halides or pseudohalides (pioneered by the Cacchi's group [39–42] ) has made great progress, [43–47] and the strategy has been used in the highly enantioselective synthesis [48–53] . We imagined whether we could control the four kinds of reactions mentioned above including C(sp 3 )−H and C(sp 2 )−H functionalizations, Heck reaction and reductive Heck reaction through variation of reaction conditions using the same kind of substrates.…”

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confidence: 99%

Base‐Controlled Palladium‐Catalyzed Intramolecular ‘One Substrate ‐ Five Reactions’ of 5‐Benzyl‐1‐(2‐halobenzyl)‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones

Liu

Zhu

Liu

et al. 2023

Chemistry A European J

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Achieving site-selectivity and chemoselectivity is enormously challenging for substrates with multi-reactive sites in organic reactions. One kind of model substrates, 5benzyl-1-(2-halobenzyl)-2-phenyl-1H-pyrazol-3(2H)-ones with six reactive sites were chosen as the examples to probe their intramolecular four kinds of five reactions including C(sp 3 )À H arylation, C(sp 2 )À H arylation, reductive Heck reaction, and domino Heck reaction/alkylation of aryl C(sp 2 )À H bonds through variation of the reaction conditions. Screening of the reaction conditions showed that the different bases controlled the palladium-catalyzed intramolecular site-selectivity and chemoselectivity of the substrates: (i) Cesium carbonate (Cs 2 CO 3 ) promoted the benzyl C(sp 3 )À H arylation of the substrates providing dihydropyrazolo[1,5-b]isoquinolin-2(1H)ones at 100 °C, and isomerization of the dihydropyrazolo[1,5-b]isoquinolin-2(1H)-ones gave isoquinoline derivatives at a higher temperature (140 °C); (ii) Sodium acetate (NaOAc) mediated the aryl C(sp 2 )À H arylation of the substrates affording seven-membered biphenyl N-heterocycles; (iii) Sodium dichloroacetate (Cl 2 HCCO 2 Na) facilitated occurrence of the reductive Heck reaction of the substrates affording 1Hpyrazolo[5,1-a]isoindol-2(8H)-ones; (iv) Sodium trifluoroacetate (F 3 CCO 2 Na) assisted performance of the domino Heck reaction/aryl C(sp 2 )À H alkylation of the substrates leading to the spiro heterocycles. The 'one substrate -multiple reactions -multiple products' strategy greatly reduces cost, increases diversity of products, provides more opportunity for screening of pharmaceutical molecules, and enriches modern organic synthetic chemistry.

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Palladium‐Catalyzed Asymmetric Reductive Heck Reaction of Aryl Halides

Abstract: Asymmetric reductive Heck reaction of aryl halides is realized in high stereoselectivity. Hydrogen-bond donors, trialkylammonium salts in a glycol solvent, were used to promote halide dissociation from neutral arylpalladium complexes to access cationic, stereoselective pathways.

Cited by 60 publications

References 104 publications

Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Palladium‐Catalyzed Suzuki–Miyaura, Heck and Hydroarylation Reactions on (–)‐Levoglucosenone and Application to the Synthesis of Chiral γ‐Butyrolactones

Base‐Controlled Palladium‐Catalyzed Intramolecular ‘One Substrate ‐ Five Reactions’ of 5‐Benzyl‐1‐(2‐halobenzyl)‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones

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