Intramolecular cyanoboration of alkynes via activation of boron–cyanide bonds by transition metal catalysts

Suginome, Michinori; Yamamoto, Akihiko; Murakami, Masahiro

doi:10.1016/j.jorganchem.2005.05.005

Cited by 36 publications

(15 citation statements)

References 34 publications

(16 reference statements)

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“…The intramolecular variation was also described [874]. Palladium catalyzed a 1,2-silaboration of allenes using an organic iodide as the initiator.…”

Section: Additions Of Hydrogen-boron -Tin -Zirconium and Miscellanmentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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“…The intramolecular variation was also described [874]. Palladium catalyzed a 1,2-silaboration of allenes using an organic iodide as the initiator.…”

Section: Additions Of Hydrogen-boron -Tin -Zirconium and Miscellanmentioning

confidence: 99%

Transition metals in organic synthesis: Highlights for the year 2005

Söderberg

2008

Coordination Chemistry Reviews

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“…The intermolecular cyanoboration is the addition of BCN bond in cyclic cyanoborane derivatives to alkynes,20, 23 while the intramolecular cyanoboration is the addition of BCN bond to carbon–carbon triple bond within the homopropargylic cyanoboryl ether 21–23. For both intermolecular and intramolecular cyanoborations, the similar cis ‐fashion products were obtained, and a possible reaction mechanism of alkyne cyanoboration was suggested by Suginome et al, which involves alkyne coordination, oxidative addition, alkyne insertion, and reductive elimination steps 22, 23. To study the mechanism of intermolecular alkynes cyanoboration, the stoichiometric reactions of cyanoboranes with palladium complexes were performed 23.…”

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

“…Recently, catalytic reactions, i.e., additions of cyanoboranes to alkynes, have been developed by Suginome et al20–23 These cyanoborations include intermolecular and intramolecular reactions. The intermolecular cyanoboration is the addition of BCN bond in cyclic cyanoborane derivatives to alkynes,20, 23 while the intramolecular cyanoboration is the addition of BCN bond to carbon–carbon triple bond within the homopropargylic cyanoboryl ether 21–23. For both intermolecular and intramolecular cyanoborations, the similar cis ‐fashion products were obtained, and a possible reaction mechanism of alkyne cyanoboration was suggested by Suginome et al, which involves alkyne coordination, oxidative addition, alkyne insertion, and reductive elimination steps 22, 23.…”

Section: Introductionmentioning

confidence: 99%

“…In the reductive elimination, both the bisphosphine and monophosphine alkenylpalladium(II) complexes are conducted. For the intramolecular reaction, the mechanism shown in Scheme is proposed by referring to the experiment22, 23 and intermolecular reaction mechanism of Scheme .…”

Section: Introductionmentioning

confidence: 99%

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Density functional study on the reaction mechanism of palladium‐catalyzed addition of cyanoboranes to alkynes

Wang

Cheng

2008

J Comput Chem

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The B3LYP hybrid density functional method has been carried out to study theoretically the mechanism of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH(3))(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH(3))(2), and in path C of each reaction, the first step is the PH(3) dissociation from Pd(PH(3))(2) to form monophosphine complex Pd(PH(3)). For both reactions, path B is favored. The dissociation and recoordination of phosphine ligand are found to be very important for the entire reaction, in agreement with the experiment. In both intermolecular and intramolecular cyanoboration reactions, cyano migration is preferred to take place compared with alkenylboryl migration for the formation of the final cis products. The rate-determining step for both intermolecular and intramolecular cyanoboration reactions is found to be the insertion of carbon-carbon triple bond into Pd-B bond with the activation energy of 38.4 and 34.3 kcal/mol relative to the initial reactants, respectively. These values suggest that intramolecular reaction is relatively easy to occur.

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Catalytic Dicyanative 5‐exo‐ and 6‐endo‐Cyclization Triggered by Cyanopalladation of Alkynes

2010

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A stereoselective dicyanative 5-exo-and 6-endo-cyclization using various enynes has been investigated. The mode of cyclization is critically controlled by the structure of the substrates. For example, N-allyl derivatives prefer 5-exo-cyclization, while methacryloyl amides are transformed to the corresponding lactams with tetra-substituted carbons at the alpha-position via 6-endo-cyclization. Both reactions include syn-cyanopalladation to carbon carbon triple bonds in the initial step, and sequential cyclization followed by reductive elimination in one operation enables the construction of the highly functionalized nitrogen heterocycles. The scope of suitable substrates and a proposed mechanism are also described.

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Intramolecular cyanoboration of alkynes via activation of boron–cyanide bonds by transition metal catalysts

Cited by 36 publications

References 34 publications

Transition metals in organic synthesis: Highlights for the year 2005

Transition metals in organic synthesis: Highlights for the year 2005

Density functional study on the reaction mechanism of palladium‐catalyzed addition of cyanoboranes to alkynes

Catalytic Dicyanative 5‐exo‐ and 6‐endo‐Cyclization Triggered by Cyanopalladation of Alkynes

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