Rhodium(I)‐Catalyzed Regiospecific Dimerization of Aromatic Acids: Two Direct CH Bond Activations in Water

Gong, Hang; Zeng, Huiying; Zhou, Feng; Li, Chao‐Jun

doi:10.1002/anie.201500220

Cited by 98 publications

(50 citation statements)

References 69 publications

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“…In recent years,s ubstantial advances in carboxylate-directed CÀHa ctivation have been made, [13] for example,b yt he groups of Yu, [14] Miura, [15] Ackermann, [16] and Larrosa, [12b,c] as well as our own group. [12d, 17] In this context, oxidative couplings of benzoic acids with alkynes to form isocoumarins,naphthalenes,and other cyclic structures have intensively been studied.…”

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confidence: 99%

Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups

et al. 2016

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In the presence of catalytic [Ru(p-cym)I 2 ] 2 and the base guanidine carbonate,b enzoica cids react with internal alkynes to give the corresponding 2-vinylbenzoic acids.T his alkyne hydroarylation is generally applicable to diversely substituted electron-rich and electron-poor benzoic and acrylic acids.A ryl(alkyl)acetylenes react regioselectively with formation of the alkyl-branched hydroarylation products,a nd propargylic alcohols are converted into g-alkylidene-d-lactones.T he hydroarylation can also be conducted decarboxylatively with ad ifferent choice of catalyst and reaction conditions.T his reaction variant, which does not proceed via intermediate formation of 2-vinylbenzoic acids,o pens up ar egioselective,w aste-minimized synthetic entry to vinylarenes.Given the prevalence of vinylarene moieties in functional materials,p harmaceuticals,a nd natural products, [1] efficient methods for the construction of this structural motif are constantly sought. Established synthetic approaches include Mizoroki-Heck [2] and Fujiwara-Moritani reactions, [3] as well as various catalytic cross-couplings of organometallic reagents with alkynes. [4] C À Hh ydroarylations of alkynes are advantageous over these processes,b ecause they require neither prefunctionalized substrates nor oxidants.S ince the pioneering studies by Murai and co-workers, [5] various metals have been found to efficiently catalyze the hydroarylation of alkynes,for example Ru, [6] Rh, [7] Re, [8] Co, [9] and others.[10] However, these CÀH functionalizations are highly regioselective only when directed by ketone,p yridine,a mide,s ulfoxide,o ro ther strong directing groups,groups which need to be synthesized in additional reaction steps and are not easily removed.Arguably,t he most advantageous directing groups in ortho-functionalizations are carboxylates,b ecause benzoic acids are widely available in great structural diversity and at low cost, and can subsequently be derivatized further, utilized as leaving groups in decarboxylative couplings, [11] or removed tracelessly by protodecarboxylation.[12] However,t he weak coordinating ability of this group poses additional challenges in the development of regiospecific CÀH-activating processes. In recent years,s ubstantial advances in carboxylate-directed CÀHa ctivation have been made, [13] for example,b yt he groups of Yu, [14] Miura, [15] Ackermann, [16] and Larrosa, [12b,c] as well as our own group. [12d, 17] In this context, oxidative couplings of benzoic acids with alkynes to form isocoumarins,naphthalenes,and other cyclic structures have intensively been studied. These reactions involve carboxylate-directed CÀHa ctivation to give vinylmetal intermediates,w hich immediately undergo cyclization steps before either reductive elimination or protonolysis can occur (Scheme 1a). [15,18] Moreover,i nt he presence of electron-deficient transition-metal catalysts or ruthenium(II), alkynes preferentially react with the nucleophilic carboxylate, to form enol esters,rather than with the CÀHmoiety...

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Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups

et al. 2016

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“…[1] Thec arboxy group,o ne of the most celebrated chelating groups,h as proven to be highly effective for assisting proximity-driven ortho-C(sp 2 )ÀHbond metalation of benzoic acids with metals such as Pd, Ru, Rh, and Ir through k 1 coordination, [2] and was pioneered by the groups of Miura and Satoh, [3a,e,f] Yu,[3c] Daugulis, [3d,p] Ackermann, [3h] Larrosa, [3j] as well as Gooßen [3m] and others (Scheme 1a). [3][4][5][6] Thei mportance of k 1 coordination of the carboxy group in promoting ortho-CÀHactivation of benzoic acids has been accounted for by Yu and co-workers,who also devised asuccessful means of shifting the equilibrium from the preferred k 2 to k 1 coordination to the Pd center by utilizing as uitable countercation such as either Na + or NR 4 + . [1d] The k 2 coordination is considered not effective for promoting the cyclometallation with ortho-C(sp 2 )ÀHb onds because of its unsuitable geometry.H owever,w eh ypothesize that this unexplored k 2 coordination mode for C(sp 2 )ÀHa ctivation can be used for delivering am etal catalyst such as Pd to recognize ar emote C À Hb ond for geometry-driven C À Ht ransformations,w hile leaving the C À Hb ond proximal to the carboxy group intact, since the carboxylate-coordinated Pd II complex prefers to adopt the k 2 coordination in the absence of ac ountercation (Scheme 1b).…”

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“…First, oxidant re-evaluation demonstrated that both AgOAc and Ag 2 CO 3 were viable oxidants but they would result in minor decarboxylation of the carboxy DG in the olefinated products;AgOPiv did not lead to decarboxylation and was therefore the optimal oxidant (Table 1, entries [5][6][7][8].…”

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Carboxy Group as a Remote and Selective Chelating Group for C−H Activation of Arenes

Wang

Weng

et al. 2019

Angew Chem Int Ed

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The first example of carboxy group assisted, remote‐selective C(sp2)−H activation with a PdII catalyst has been developed and proceeds through a possible κ2 coordination of the carboxy group, thus suppressing the ortho‐C−H activation through κ1 coordination. Besides meta‐C−H olefination, direct meta‐arylation of hydrocinnamic acid derivatives with low‐cost aryl iodides has been achieved for the first time. These findings may motivate the exploration of novel reactivities of the carboxy assisted C−H activation reactions with intriguing selectivities.

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“…[1] Initially, this approach was often limited by the use of complex directing groups, [2] which needed to be installed and later removed, thus adding steps to the overall process.Instate-ofthe-art methods,t he selectivity can be enforced even by ubiquitous functionalities,i ncluding ketone, [3] hydroxy, [4] or carboxylate groups. [6] Inspired by pioneering work by Miura and co-workers, [7] ah uge variety of carboxylatedirected sp 2 CÀH ortho-functionalizations have been developed for example,b yt he groups of Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] our group, [15] and others. [6] Inspired by pioneering work by Miura and co-workers, [7] ah uge variety of carboxylatedirected sp 2 CÀH ortho-functionalizations have been developed for example,b yt he groups of Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] our group, [15] and others.…”

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Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds

Zhang

Belitz

et al. 2019

Angew Chem Int Ed

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In the presence of a[Cp*RhCl 2 ] 2 catalyst, the Lewis acid In(OTf) 3 ,a nd the mild base Na 2 CO 3 ,a romatic carboxylates and a,b-unsaturated ketones undergo au nique hydroarylation/Claisen/retro-Claisen process to give the corresponding indanones.I nt his carboxylate-directed ortho-CÀHa nnelation, the C À COR bond of the ketone and the CO À OH group of the aromatic carboxylate are cleaved, and the hydroxy group is transferred from the aromatic to the aliphatic acyl residue. This reactivity is synthetically useful, particularly when starting from cyclic ketones,w hich are converted into indanones bearing aliphatic carboxylate side chains,thus greatly increasing the molecular complexity of aromatic carboxylates in asingle step.Scheme 3. Preferential formation of diketones at incomplete conversion. Scheme 4. Mechanistic investigations. Angewandte Chemie Communications

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Rhodium(I)‐Catalyzed Regiospecific Dimerization of Aromatic Acids: Two Direct CH Bond Activations in Water

Cited by 98 publications

References 69 publications

Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups

Regioselective C−H Hydroarylation of Internal Alkynes with Arenecarboxylates: Carboxylates as Deciduous Directing Groups

Carboxy Group as a Remote and Selective Chelating Group for C−H Activation of Arenes

Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds

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