Branch-Selective and Enantioselective Iridium-Catalyzed Alkene Hydroarylation via Anilide-Directed C–H Oxidative Addition

Grélaud, Simon; Cooper, Phillippa; Feron, Lyman; Bower, John F.

doi:10.1021/jacs.8b04627

Cited by 113 publications

(69 citation statements)

References 56 publications

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“…[1] Currently,t he hydroarylation of styrenes and the Friedel-Crafts alkylation of benzylic alcohols are among the methods of choice for the synthesis of diaryl alkanes. [3] As ar esult, the synthesis of diaryl alkanes incorporating strongly electron withdrawing groups is difficult, thus denying access to potentially useful compounds. [3] As ar esult, the synthesis of diaryl alkanes incorporating strongly electron withdrawing groups is difficult, thus denying access to potentially useful compounds.…”

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confidence: 99%

“…[2] However,t hese approaches have am ajor drawback:T he presence of electron-donating groups or, at best, moderately electron withdrawing groups on the aromatic ring is usually necessary to trigger the reaction, although in some cases this limitation can be overcome with tailor-made transition-metalbased systems. [3] As ar esult, the synthesis of diaryl alkanes incorporating strongly electron withdrawing groups is difficult, thus denying access to potentially useful compounds. Only ah andful of methods to generate these types of frameworks have been developed, all of which bear their own limitations.…”

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confidence: 99%

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Calcium(II)‐Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol

Gandon

Lebœuf

2018

Angew Chem Int Ed

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A challenging catalytic hydroarylation of highly electron deficient styrenes has been developed on the basis of efficient cooperation between a calcium(II) triflimide salt and hexafluoroisopropanol (HFIP). This method affords a large variety of diaryl alkanes, notably diaryl ethanes, in good to excellent yields, and is simple to implement and compatible with various functional groups. Furthermore, DFT calculations and deuterium labeling experiments were conducted to elucidate the function of this promoter system.

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confidence: 99%

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confidence: 99%

Calcium(II)‐Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol

Gandon

Lebœuf

2018

Angew Chem Int Ed

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“…Then, L4 was tested and the reaction gave the desired product 2 a in 66 % yield with 69 % ee (entry 4). BiPhePhos‐like ligand L5 , which was first reported by Bower in a C−H bond functionalization reaction, afforded 2 a in 60 % yield with 94 % ee (entry 5). When changing the ligand configuration ( L6 ), we noted both a lower yield and ee in the desired product 2 a , with opposite configuration compared to L5 (entry 6).…”

Section: Figurementioning

confidence: 97%

Access to 1,3‐Dinitriles by Enantioselective Auto‐tandem Catalysis: Merging Allylic Cyanation with Asymmetric Hydrocyanation

Long

Gao

et al. 2020

Angewandte Chemie

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Enantioselective auto‐tandem catalysis represents a challenging yet highlight attractive topic in the field of asymmetric catalysis. In this context, we describe a dual catalytic cycle that merges allylic cyanation and asymmetric hydrocyanation. The one‐pot conversion of a broad array of allylic alcohols into their corresponding 1,3‐dinitriles proceeds in good yield with high enantioselectivity. The products are densely functionalized and can be easily transformed to chiral diamines, dinitriles, diesters, and piperidines. Mechanistic studies clearly support a novel sequential cyanation/hydrocyanation pathway.

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“…It is known that in pyridines, the C2 position is more facile for functionalization than other positions (C3, C4) mainly due to the larger acidity of the C2−H bond and the stronger electrophilic character of the C2=N moiety. Therefore, the successful access of pyridine derivatives via various catalytic and non‐catalytic methods is basically limited to functionalization at the C2‐position. Thus the regioselective and further enantioselective functionalizations at the 3‐ and 4‐positions of pyridines keep a great challenge.…”

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confidence: 99%

Mechanism and Origin of MAD‐Induced Ni/N‐Heterocyclic Carbene‐Catalyzed Regio‐ and Enantioselective C−H Cyclization of Pyridines with Alkenes

Zhao

Zhu

et al. 2020

Chemistry A European J

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This work presentsaDFT-based computational study on the regio-ande nantioselective CÀHf unctionalization of pyridines with alkenes at the relatively unreactiveC 4position, whichw as successfully achieved by Shi et al. [J. Am. Chem. Soc. 2019, 141,5 628-5634] using Ni 0 /N-heterocyclic carbene( NHC) catalysis undert he assistanceo fa na luminum-based Lewis acid additive (2,6-tBu 2 -4-Me-C 6 H 2 O) 2 AlMe (MAD).T he calculationsi ndicate that the selectivef unctionalizationi nvolves at hree-step mechanism in whichaunique H-migration assisted oxidation metalation( HMAOM) step is identified as the rate-and enantioselectivity-determining step. The newly proposed mechanism can well rationalize the experimental observation that the preferred product is the endo-type (vs. exo-type), R-configuration (vs. S-configuration) product at the C4 (vs. C2) position, and also unveil the reasons that the NHC ligand and the MAD additive can facilitate the reaction.[a] X.Scheme1.Arepresentative example of MAD-induced Ni 0 /NHC-catalyzed regio-and enantioselective CÀHc yclization of alkene-tethered pyridine 1 reported by Shi and co-workers. [29] Scheme2.Proposed reaction pathway by Shi et al. [29] for the Ni 0 -catalyzed regio-a nd enantioselectiveC ÀHa ctivationa tt he C4-positiono falkene-tethered pyridine (1). Figure 7. (a) Geometries and the relativee nergies (in kcal mol À1 )o fkey intermediates and rate-determining transitions tates for the endo-type cyclization at the C4-position in the Ni 0 -catalyzed reaction with and without presence of the NHC ligand, and (b) HOMOs andLUMOso fNi(cod),p yridine-MAD adduct 3, and Ni(NHC).

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Branch-Selective and Enantioselective Iridium-Catalyzed Alkene Hydroarylation via Anilide-Directed C–H Oxidative Addition

Abstract: Tertiary benzylic stereocenters are accessed in high enantioselectivity by Ir-catalyzed branch selective addition of anilide ortho-C-H bonds across styrenes and α-olefins. Mechanistic studies indicate that the stereocenter generating step is reversible.

Cited by 113 publications

References 56 publications

Calcium(II)‐Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol

Calcium(II)‐Catalyzed Intermolecular Hydroarylation of Deactivated Styrenes in Hexafluoroisopropanol

Access to 1,3‐Dinitriles by Enantioselective Auto‐tandem Catalysis: Merging Allylic Cyanation with Asymmetric Hydrocyanation

Mechanism and Origin of MAD‐Induced Ni/N‐Heterocyclic Carbene‐Catalyzed Regio‐ and Enantioselective C−H Cyclization of Pyridines with Alkenes

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