A New Solvent System for Recycling Catalysts for Chelation‐Assisted Hydroacylation of Olefins with Primary Alcohols.

Chang, Duck‐Ho; Lee, Dae‐Yon; Hong, Boo‐Sun; Choi, Jun‐Hack; Jun, Chul Ho

doi:10.1002/chin.200421063

Cited by 3 publications

(3 citation statements)

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“…A mixture of 4,4′-bipyridine and phenol can be utilized as a hydrogen-bonding solvent to simplify the process by liberating both the metal and the organic catalysts and generating the alkane or alkene at room temperature (Figure 2). 89 Hydroacylation of alkene 22 with primary alcohol 51 takes place using this hydrogen-bonding solvent system to afford ketone 24.…”

Section: Reaction Of Alcohol With Alkenementioning

confidence: 99%

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

2017

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Transition-metal-catalyzed activation of C-H and C-C bonds is a challenging area in synthetic organic chemistry. Among various methods to accomplish these processes, the approach using metal-organic cooperative catalytic systems is one of the most promising. In this protocol, organic molecules as well as transition metals act as catalysts to bring about reactions, which proceed with high efficiencies and selectivities. Various metal-organic cooperative catalytic systems developed for C-H and C-C bond activation reactions are discussed in this review. Also discussed are how each metal-organic cooperative catalyst affects the reaction mechanism and what kinds of substrates can be applied in each of the catalytic processes.

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Section: Reaction Of Alcohol With Alkenementioning

confidence: 99%

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

2017

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“…Based on the fact that phenol and 4,4′-dipyridyl form a hydrogen-bonding complex, 37 a mixed solvent system was conceived as a reaction medium for the hydroacylation of primary alcohols. 38 Interestingly, this solvent system forms two immiscible phases with hydrocarbons such as alkane or olefin at room temperature. Because a strong hydrogen-bonding network is hardly at high temperature, these two phases combine into one phase upon heating (Figure 2a).…”

Section: Hydrogen-bonded Self-assemblies As a Metal-organic Catalyst ...mentioning

confidence: 99%

Metal−Organic Cooperative Catalysis in C−H and C−C Bond Activation and Its Concurrent Recovery

2008

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The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic components using a hydrogen-bonded self-assembled system as a catalyst support. This catalyst-recovery system provides a homogeneous phase at high temperature during the reaction and a heterogeneous phase at room temperature after the reaction. The product could be separated conveniently from the self-assembly support system by decanting the upper layer. The immobilized catalysts of both 2-aminopyridine and rhodium metal species sustained high catalytic activity for up to the eight catalytic reactions. In conclusion, the successful incorporation of an organocatalytic cycle into a transition metal catalyzed reaction led us to find MOCC for C-H and C-C bond activation. In addition, the hydrogen-bonded self-assembled support has been developed for an efficient and effective recovery system of homogeneous catalysts and could be successful in immobilizing both metal and organic catalysts.

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“…The recyclability of the catalysts was demonstrated by running the reaction four times without any loss of activity. The group also previously reported a new solvent system for recycling catalysts 385 and also in 2006 a report on the employment of a recyclable self-assembly supported catalyst for this reaction. 386 Later on, the same group employed vinylsilane coupling reactions for the immobilization of organic functional groups onto silica solid supports.…”

Section: Cofactor Assisted C−c Bond Activation Via Imine Intermediatementioning

confidence: 93%

Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis

2016

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The cooperation and interplay between organic and metal catalyst systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The transition metal catalyst complements by activating a variety of substrates through a range of interactions (e.g., electrophilic π-allyl complex formation, Lewis acid activation, allenylidene complex formation, photoredox activation, C-H activation, etc.), and thereby novel concepts within catalysis are created. The inclusion of heterogeneous catalysis strategies allows for "green" chemistry development, catalyst recyclability, and the more eco-friendly synthesis of valuable compounds.

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A New Solvent System for Recycling Catalysts for Chelation‐Assisted Hydroacylation of Olefins with Primary Alcohols.

Cited by 3 publications

References 1 publication

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

Metal–Organic Cooperative Catalysis in C–H and C–C Bond Activation

Metal−Organic Cooperative Catalysis in C−H and C−C Bond Activation and Its Concurrent Recovery

Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis

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