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1.
Org Lett ; 22(2): 417-421, 2020 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-31895577

RESUMO

A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis-fused [5,5] bicyclic γ-lactones and γ-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels-Alder reaction with N-phenylmaleimide, providing polycyclic compounds with increased molecular complexity.

2.
Chemistry ; 26(15): 3241-3246, 2020 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-31875327

RESUMO

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF3 radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C-H trifluoromethylations of unactivated arenes and heteroarenes. The robust nature of the electrophotochemical manifold was reflected by a wide scope, including electron-rich and electron-deficient benzenes, as well as naturally occurring heteroarenes. Electrophotochemical C-H trifluoromethylation was further achieved in flow with a modular electro-flow-cell equipped with an in-operando monitoring unit for on-line flow-NMR spectroscopy, providing support for the single electron transfer processes.

3.
J Am Chem Soc ; 141(6): 2731-2738, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30636408

RESUMO

Electrochemical C-C activations were accomplished by expedient oxidative rhodium(III) catalysis. Thus, oxidative C-C alkenylations proved viable with the aid of electricity, avoiding the use of toxic and/or expensive transition-metal oxidants. The chelation-assisted C-C functionalizations proceeded with ample scope and excellent levels of chemo- and position selectivities within an organometallic C-C activation manifold. Detailed mechanistic studies provided support for a kinetically relevant C-C scission, and a well-defined organometallic rhodium(III) complex was identified as a catalytically competent intermediate. The electrochemical C-C functionalization was devoid of additional electrolytes, could be conducted on a gram scale, and provided position-selective access to densely 1,2,3-substituted arenes, which are not viable by C-H activation.

4.
Chemistry ; 25(1): 210-215, 2019 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-30307089

RESUMO

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.

5.
J Am Chem Soc ; 140(43): 14324-14333, 2018 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-30281287

RESUMO

A highly selective palladium-catalyzed hydroborylative carbocyclization of bisallenes to afford seven-membered rings has been established. This ring-closing coupling reaction showed good functional group compatibility with high chemo- and regioselectivity, as seven-membered ring 3 was the only product obtained. The extensive use of different linkers, including nitrogen, oxygen, malononitrile, and malonate, showed a broad substrate scope for this approach. A one-pot cascade reaction was realized by trapping the primary allylboron compound with an aldehyde, affording a diastereomerically pure alcohol and a quaternary carbon center by formation of a new C-C bond. A comprehensive mechanistic DFT investigation is also presented. The calculations suggest that the reaction proceeds via a concerted hydropalladation pathway from a Pd(0)-olefin complex rather than via a pathway involving a defined palladium hydride species. The reaction was significantly accelerated by the coordination of the pendant olefin, as well as the introduction of suitable substituents in the bridge, due to the Thorpe-Ingold effect.

6.
J Am Chem Soc ; 140(44): 14604-14608, 2018 11 07.
Artigo em Inglês | MEDLINE | ID: mdl-30358399

RESUMO

A palladium-catalyzed oxidative tandem process of enallenols was accomplished within a homogeneous/heterogeneous catalysis manifold, setting the stage for the highly chemodivergent and diastereoselective synthesis of γ-lactones and γ-lactams under mild conditions.

7.
Angew Chem Int Ed Engl ; 57(43): 14179-14183, 2018 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-30199130

RESUMO

Iridium-catalyzed electrochemical C-H activation was accomplished within a cooperative catalysis manifold, setting the stage for electrooxidative C-H alkenylations through weak O-coordination. The iridium-electrocatalyzed C-H activation featured high functional-group tolerance through assistance of a metal-free redox mediator through indirect electrolysis. Detailed mechanistic insights provided strong support for an organometallic C-H cleavage and a synergistic iridium(III/I)/redox catalyst regime, enabling the use of sustainable electricity as the terminal oxidant with improved selectivity features.

8.
Chemistry ; 24(49): 12784-12789, 2018 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-29901828

RESUMO

Catalyst- and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3 )-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant.

9.
Acc Chem Res ; 51(6): 1520-1531, 2018 06 19.
Artigo em Inglês | MEDLINE | ID: mdl-29792667

RESUMO

Oxidation reactions play a central role in organic synthesis, and it is highly desirable that these reactions are mild and occur under catalytic conditions. In Nature, oxidation reactions occur under mild conditions via cascade processes, and furthermore, they often occur in an enantioselective manner with many of them involving molecular oxygen or hydrogen peroxide as the terminal oxidant. Inspired by the reactions in Nature, we have developed a number of Pd(II)-catalyzed cascade reactions under mild oxidative conditions. These reactions have an intrinsic advantage of step economy and rely on selectivity control in each step. In this Account, we will discuss the control of chemo-, regio-, and diastereoselectivity in Pd(II)-catalyzed dehydrogenative cascade coupling reactions. The enantioselective version of this methodology has also been addressed, and new chiral centers have been introduced using a catalytic amount of a chiral phosphoric acid (CPA). Research on this topic has provided access to important compounds attractive for synthetic and pharmaceutical chemists. These compounds include carbocyclic, heterocyclic, and polycyclic systems, as well as polyunsaturated open-chain structures. Reactions leading to these compounds are initiated by coordination of an allene and an unsaturated π-bond moiety, such as olefin, alkyne, or another allene, to the Pd(II) center, followed by allene attack involving a C(sp3)-H cleavage under mild reaction conditions. Recent progress within our research group has shown that weakly coordinating groups (e.g., hydroxyl, alkoxide, or ketone) could also initiate the allene attack on Pd(II), which is essential for the oxidative carbocyclization. Furthermore, a highly selective palladium-catalyzed allenic C(sp3)-H bond oxidation of allenes in the absence of an assisting group was developed, which provides a novel and straightforward synthesis of [3]dendralene derivatives. For the oxidative systems, benzoquinone (BQ) and its derivatives are commonly used as oxidants or catalytic co-oxidants (electron transfer mediators, ETMs) together with molecular oxygen. A variety of transformations including carbocyclization, acetoxylation, arylation, carbonylation, borylation, ß-hydride elimination, alkynylation, alkoxylation, and olefination have been demonstrated to be compatible with this Pd(II)-based catalytic oxidative system. Recently, several challenging synthetic targets, such as cyclobutenes, seven-membered ring carbocycles, spirocyclic derivatives, functional cyclohexenes, and chiral cyclopentenone derivatives were obtained with high selectivity using these methods. The mechanisms of the reactions were mainly studied by kinetic isotope effects (KIEs) or DFT computations, which showed that in most cases the C(sp3)-H cleavage is the rate-determining step (RDS) or partially RDS. This Account will describe our efforts toward the development of highly selective and atom-economic palladium(II)-catalyzed oxidative transformation of allenes (including enallenes, dienallenes, bisallenes, allenynes, simple allenes, and allenols) with a focus on overcoming the selectivity problem during the reactions.

10.
Angew Chem Int Ed Engl ; 57(20): 5828-5832, 2018 05 14.
Artigo em Inglês | MEDLINE | ID: mdl-29633454

RESUMO

Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we herein describe the first electrochemical rhodium-catalyzed C-H activation that avoids hazardous chemical oxidants. Environmentally benign twofold C-H/C-H functionalizations were accomplished with weakly coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant and generating H2 as the sole byproduct.

11.
Angew Chem Int Ed Engl ; 57(20): 5818-5822, 2018 05 14.
Artigo em Inglês | MEDLINE | ID: mdl-29603565

RESUMO

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate.

12.
J Am Chem Soc ; 140(9): 3210-3214, 2018 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-29425445

RESUMO

A highly diastereoselective palladium-catalyzed oxidative carbocyclization-borylation of enallenes assisted by a weakly coordinating hydroxyl group was developed. The reaction afforded functionalized cyclohexenol derivatives, in which the 1,3-relative stereochemistry is controlled (d.r. > 50:1). Other weakly coordinating oxygen-containing groups (ketone, alkoxide, acetate) also assisted the carbocyclization toward cyclohexenes. The reaction proceeds via a ligand exchange on Pd of the weakly coordinating group with a distant olefin group. The high diastereoselectivity of the hydroxyl-directed reaction could be rationalized by a face-selective coordination of the distant olefin. It was demonstrated that the primary coordination of the close-by oxygen-containing functionality was necessary for the reaction to occur and removal of this functionality shut down the reaction.

13.
Chemistry ; 24(10): 2433-2439, 2018 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-29266429

RESUMO

The asymmetric palladium-catalyzed oxidative carbocyclization-borylation of enallenes, employing a chiral phosphoric acid as co-catalyst, constitutes an efficient and convenient entry into functionalized building blocks with cyclopentene scaffolds in high enantiopurity. Up till now there has been a lack of knowledge concerning the origin of enantioselectivity of this reaction as well as the absolute configuration of the product. Herein, we report the crystal structure of one of the compounds generated via this carbocyclization, providing the link between the configuration of the products and the configuration of the chiral phosphoric acid used in the reaction. Furthermore, the origin of the enantioselectivity is thoroughly investigated with density functional theory (DFT) calculations. By careful examination of different possible coordination modes, it is shown that the chiral phosphoric acid and the corresponding phosphate anion serve as ligands for palladium during the key stereoselectivity-determining cyclization step. In addition, we examine reactions wherein an extra chiral reagent, a p-benzoquinone containing a chiral sulfoxide, is used. The combined experimental and theoretical studies provide insight into the details of complexation of palladium with various species present in the reaction mixture, furnishing a general understanding of the factors governing the stereoselectivity of this and related catalytic reactions.

14.
Angew Chem Int Ed Engl ; 56(42): 13112-13116, 2017 10 09.
Artigo em Inglês | MEDLINE | ID: mdl-28799682

RESUMO

A highly selective palladium-catalyzed allenic C-H bond oxidation was developed, and it provides a novel and straightforward synthesis of [3]dendralene derivatives. A variety of [3]dendralenes with diverse substitution patterns are accessible with good efficiency and high stereoselectivity. The reaction tolerates a broad substrate scope containing various functional groups on the allene moiety, including ketone, aldehyde, ester, and phenyl groups. Also, a wide range of olefins with both electron-donating and electron-withdrawing aryls, acrylate, sulfone, and phosphonate groups are tolerated.

15.
Chem Sci ; 8(1): 616-620, 2017 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-28616136

RESUMO

A highly selective olefin-assisted palladium-catalyzed oxidative carbocyclization via remote olefin insertion to afford cyclohexenes has been developed. It was shown that the assisting olefin moiety was indispensable for the formation of the cyclohexene product. Furthermore, preliminary studies on chiral anion-induced asymmetrical carbocyclization-borylation of enallenes have been carried out.

16.
Chem Commun (Camb) ; 53(34): 4722-4725, 2017 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-28401967

RESUMO

An unexpected PtCl4-catalyzed cyclization reaction of tertiary indol-2-yl-3-alkynols occurred smoothly in toluene to form various poly-substituted carbazole derivatives efficiently. A possible mechanism involving the formation of a spiro-tricyclic intermediate via indole C-2 attack, highly selective ring expansion and then 1,2-migration has been proposed for the formation of carbazoles.

17.
Chemistry ; 23(33): 7896-7899, 2017 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-28440882

RESUMO

An olefin-assisted, palladium-catalyzed oxidative alkynylation of enallenes for regio- and stereoselective synthesis of substituted trienynes has been developed. The reaction shows a broad substrate scope and good tolerance for various functional groups on the allene moiety, including carboxylic acid esters, free hydroxyls, imides, and alkyl groups. Also, a wide range of terminal alkynes with electron-donating and electron-withdrawing aryls, heteroaryls, alkyls, trimethylsilyl, and free hydroxyl groups are tolerated.

18.
Angew Chem Int Ed Engl ; 56(16): 4535-4539, 2017 04 10.
Artigo em Inglês | MEDLINE | ID: mdl-28345175

RESUMO

An enantioselective PdII /Brønsted acid-catalyzed carbonylative carbocyclization of enallenes ending with a cross-dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co-catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α-chiral ketones. As a result, a number of chiral cyclopentenones were easily synthesized in good to excellent enantiomeric ratio with good yields.

19.
Angew Chem Int Ed Engl ; 56(12): 3221-3225, 2017 03 13.
Artigo em Inglês | MEDLINE | ID: mdl-28211212

RESUMO

A highly selective palladium-catalyzed oxidative carbonylation/carbocyclization/alkoxycarbonylation of enallenols to afford spirolactones bearing an all-carbon quaternary center was developed. This transformation involves the overall formation of three C-C bonds and one C-O bond through a cascade insertion of carbon monoxide (CO), an olefin, and CO. Preliminary experiments on chiral anion-induced enantioselective carbonylation/carbocyclization of enallenols afforded spirolactones with moderate enantioselectivity.

20.
J Am Chem Soc ; 138(42): 13846-13849, 2016 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-27704805

RESUMO

A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C-C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C-C bonds.

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