Synthesis of Cycloalkanones from Dienes and Allylamines Through C—H and C—C Bond Activation Catalyzed by a Rhodium(I) Complex.

Lee, Dae‐Yon; Kim, In‐Jung; Jun, Chul Ho

doi:10.1002/chin.200250035

Cited by 8 publications

(10 citation statements)

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“…A metal–organic cooperative catalysis strategy for C–H and C–C bond activation reactions has been applied to the preparation of cycloalkanones from allyl amines (Scheme ). For instance, reaction of allyl amine 174 with diene 175 under cooperative catalysis by Rh(I) complex 66 , Cy 3 P, and 2-amino-3-picoline ( 11 ) affords a mixture of cycloheptanone ( 176 ) and α-methylcyclohexanone ( 177 ) in a 53/47 ratio. The proposed mechanism of this reaction begins with formation of aldimine 171 from allyl amine 174 through Rh(I)-catalyzed olefin isomerization, followed by transimination with 11 .…”

Section: Cooperative Catalysis By 2-amino-3-picoline and Rhodium(i) C...mentioning

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: Cooperative Catalysis By 2-amino-3-picoline and Rhodium(i) C...mentioning

confidence: 99%

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

2017

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“…For example, reaction of allylamine 78 with diene 79 in the presence of rhodium catalyst and 2-amino-3-picoline (21) produces, after acidic hydrolysis, a mixture of cycloheptanone 80 and α-methylcyclohexanone 81 (Scheme 14a) [32]. C-C bond activation in this reaction occurs on ketimine 82, which is formed by a sequence (Scheme 14b) involving Rh(I)-catalyzed isomerization of allylamine 78 to generate corresponding imine 80 followed by transimination of 80 with 21 to produce imine 75.…”

Section: Metal-organic Cooperative C-c Single Bond Cleavagementioning

confidence: 99%

Metal–Organic Cooperative Catalysis in C–C Bond Activation

Jun

Park

2013

Topics in Current Chemistry

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This review describes recent advances that have been made in studies of transition metal-promoted metal-organic cooperative C-C single bond activation reactions of unstrained organic substances, which use 2-aminopicoline as a temporal chelating ligand. In addition, metal-organic cooperative C-C double bond and C-C triple bond cleavage processes are discussed in association with transition metal-catalyzed C-H bond activation. Recent progress made in these areas has opened up the new paradigms in synthetic organic chemistry for the construction of organic frameworks by structural reorganization of organic backbones. Among the many strategies devised, chelation-assisted C-C bond cleavage reactions, which operate through cooperation between metal complexes and organic substances, have attracted perhaps the greatest attention. Utilizing this approach, efficient C-C single bond activation reactions have been developed for a variety of substrates, including linear alkyl ketones, secondary alcohols, primary amines, and cycloalkanones. In addition, reactions that lead to cleavage of C-C double and triple bonds can be facilitated by using the metal-organic cooperation strategy. C-C double bonds in α,β-enones can be cleaved by addition of cyclohexylamine, which facilitates Michael addition and retro-Mannich type fragmentation cascades proceeding via β-aminoketimine intermediates. Aldehydes, which serve as one of the fragmentation products of these processes, can be trapped by chelation-assisted hydroacylation reactions to produce ketones. Finally, C-C triple bond cleavage of alkynes can be achieved through hydroacylation reactions with aldehydes and subsequent C-C double bond cleavage of the resulting α,β-enones.

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“…Moreover, the same group reported the use of dienes in place of olefins as the coupling partner to react with allylic amines, providing a new access to various cycloalkanones. 60 In this case, the allylic amine served as a masked formaldehyde to provide a one-carbon unit. All 1,3-, 1,4and 1,5-dienes were efficiently coupled to afford cycloalkanones in a ring-size of five to seven.…”

Section: Dgs Removed Via Post-chemical Transformationsmentioning

confidence: 99%

Temporary or removable directing groups enable activation of unstrained C–C bonds

2020

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Carbon−carbon (C-C) bonds constitute basic skeletons in most organic molecules. One can imagine that selective manipulation of C-C bonds would provide a direct approach to edit or alter molecular scaffolds but has been an ongoing challenge. Due to the kinetic inertness of C-C bonds, the common strategies of activating these bonds by transition metals rely on either the use of highly strained substrates or the assistance of a permanent directing group (DG), in which strain relief or formation of stable metallocycles becomes the driving force. To allow more common and less strained compounds utilized as substrates for C-C activation, the use of temporary and removable DGs has emerged as an attractive strategy in the past two decades. A variety of C−C bonds in unstrained or less strained organic molecules now can be converted to more reactive metal-carbon bonds, and further downstream transformations have led to diverse synthetic methods. This review highlights the development of catalytic approaches that can activate unstrained C-C bonds enabled by temporary or removable DGs. The content is mainly divided based on the nature of the DGs: temporary and removable. Applications of these methods in syntheses of natural products or bioactive molecules are also discussed.

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Synthesis of Cycloalkanones from Dienes and Allylamines Through C—H and C—C Bond Activation Catalyzed by a Rhodium(I) Complex.

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 8 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–C Bond Activation

Temporary or removable directing groups enable activation of unstrained C–C bonds

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