Rhodium-Catalyzed Oxidative <i>ortho</i>-Acylation of Benzamides with Aldehydes: Direct Functionalization of the sp<sup>2</sup> C–H Bond

Park, Jihye; Park, Eonjeong; Kim, Aejin; Lee, Youngil; Chi, Ki‐Whan; Kwak, Jong Hwan; Jung, Young Hoon; Kim, In Su

doi:10.1021/ol201729w

Cited by 162 publications

(43 citation statements)

References 65 publications

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“…Lower temperature suppressed the efficiency, whereas higher temperature did not lead to a better outcome (cf. [19][20][21][22][23][24][25]. In general, protic solvents were better than nonprotic solvents in terms of efficiency.…”

Section: Resultsmentioning

confidence: 99%

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Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl‐directed Rh‐catalyzed CC bond cleavage of secondary alcohols and subsequent addition to CX (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of CC bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in‐depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron‐rich alcohols and electron‐deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the CC bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The CC cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the CC cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of CC cleavage/nucleophilic addition and CC cleavage/protonation/CH activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the “group transplant”, this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.

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Section: Resultsmentioning

confidence: 99%

“…[13] Especially, Rh catalysis has played an important role in this field. [14][15][16][17][18][19][20] In addition, Rh catalysts have also been used in other types of C À H functionalization reactions. [21][22][23] These transformations are relatively benign to the environment.…”

Section: Introductionmentioning

confidence: 99%

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Zhang¹,

Li²,

Li³

et al. 2012

Chemistry A European J

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“…In their study, tertiary benzamides 63 were coupled with aromatic aldehydes using silver carbonate (Ag 2 CO 3 ) as the stoichiometric oxidant (Scheme 30). 46 The influence of the amide directing group on the reaction outcome was also explored. While the N , N -dimethyl, N , N -diethyl, and pyrrolidine amides provided comparable reactivity, the sterically hindered N , N -dibenzyl and electron-deficient morpholine amide derivatives coupled in low yield.…”

Section: Aldehydesmentioning

confidence: 99%

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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The transition metal-catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functionality group compatibility and without the production of waste byproducts. Additionally, many transition metal-catalyzed C–H bond additions to polarized π-bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition metal catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds.

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“…[1][2][3][4][5][6][7][8][9][10][11] In this context, pyrazole serves as an effective directing group for C-H functionalization methods involving cyclometalation. But, at present, methods for directed C-H acylation of 1-arylpyrazole 12 are relatively scarce while there are numerous reports on directed C-H acylation of 2-phenyl pyridine (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Palladium nanoparticles supported on organofunctionalized kaolin as an efficient heterogeneous catalyst for directed C–H functionalization of arylpyrazoles

Yang

Bao

2017

RSC Adv.

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Rhodium-Catalyzed Oxidative ortho-Acylation of Benzamides with Aldehydes: Direct Functionalization of the sp² C–H Bond

Cited by 162 publications

References 65 publications

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Palladium nanoparticles supported on organofunctionalized kaolin as an efficient heterogeneous catalyst for directed C–H functionalization of arylpyrazoles

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Rhodium-Catalyzed Oxidative ortho-Acylation of Benzamides with Aldehydes: Direct Functionalization of the sp2 C–H Bond

Cited by 162 publications

References 65 publications

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Rh‐Catalyzed CC Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Palladium nanoparticles supported on organofunctionalized kaolin as an efficient heterogeneous catalyst for directed C–H functionalization of arylpyrazoles

Contact Info

Product

Resources

About

Rhodium-Catalyzed Oxidative ortho-Acylation of Benzamides with Aldehydes: Direct Functionalization of the sp² C–H Bond