DFT Studies of Alkene Insertions into Cu−B Bonds in Copper(I) Boryl Complexes

Dang, Li; Zhao, Haitao; Lin, Zhenyang; Marder, Todd B.

doi:10.1021/om070103r

Cited by 218 publications

(134 citation statements)

References 87 publications

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“…Olefin insertion should readily occur in the presence of alkene B and CuH catalyst A to generate Cu(I)-alkyl C . In line with previous work, 12 we believed that olefin insertion should occur in an anti-Markovnikov fashion with a simple α-olefin. Concomitant oxidative addition of Pd(0) D into aryl electrophile E would generate Pd(II) aryl complex F .…”

supporting

confidence: 89%

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross‐Coupling of Aryl Halides and Olefins

et al. 2017

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We report an efficient means of sp –sp cross coupling for a variety of terminal monosubstituted olefins with aryl electrophiles using Pd and CuH catalysis. In addition to its applicability to a range of aryl bromide substrates, this process was also suitable for electron-deficient aryl chlorides, furnishing higher yields than the corresponding aryl bromides in these cases. The optimized protocol does not require the use of a glovebox and employs air-stable Cu and Pd complexes as precatalysts. A reaction on 10 mmol scale further highlighted the practical utility of this protocol. Employing a similar protocol, a series of cyclic alkenes were also examined. Cyclopentene was shown to undergo efficient coupling under these conditions. Lastly, deuterium-labeling studies indicate that deuterium scrambling does not take place in this sp2–sp3 cross coupling, implying that β-hydride elimination is not a significant process in this transformation.

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supporting

confidence: 89%

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross‐Coupling of Aryl Halides and Olefins

et al. 2017

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“…In other words, for the allene insertion into PdÀ ÀSi bond, the electron back-donation is significant, which was also observed in the CO 2 (ref. 40) or alkene 41 insertion into CuÀ ÀB bond. Thus, it should be reasonable to examine only the orientation of the electron transfer in the back-donation process for both terminal-and internal-insertion.…”

Section: Allene Coordination and Insertionmentioning

confidence: 99%

Reaction mechanism of palladium‐catalyzed silastannation of allenes by density functional theory

et al. 2008

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The reaction mechanism of Pd(0)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed in terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

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“…31 The Wachters basis set combined with 6-31G*, and the augmented Wachters set combined with 6-3111G(2d,2p), were used in several studies of copper(I) complexes. [32][33][34] These studies showed that while B3LYP yields relatively good geometries [32][33][34] it leads to significant overestimation of binding energies. Thus, ab initio methods such as CCSD(T) and possibly MP2 are suggested to obtain accurate binding energies.…”

Section: Introductionmentioning

confidence: 99%

Can DFT methods correctly and efficiently predict the coordination number of copper(I) complexes? A case study

et al. 2009

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The coordination number of various experimentally known Cu(I) compounds is studied using density functional theory. Various basis sets are tested, aiming to establish a reliable level for prediction of the coordination number of these and other Cu(I) complexes. It is found that most levels exhibit correct trends, namely, the bulkier ligands demonstrate larger preference for coordination of two ligands. Proper absolute values are obtained when dispersion corrections are also included in the calculations. It is concluded that the fairly small modified 6-31+G* basis set due to Pulay represents a good compromise between accuracy and efficiency, followed by Balabanov and Peterson's all-electron aug-cc-pVDZ basis set. The overall energy is decomposed into various components whose relative contribution to the overall tendency of forming a complex with a particular coordination is examined. It is shown that two opposing contributions play a major role: the interaction energy of the ligand being added and the deformation energy of the copper's coordination sphere prior to the ligand addition. The former being a stabilizing contribution, leads to higher coordination numbers while the later, a destabilizing contribution, is shown to favor lower coordination numbers.

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DFT Studies of Alkene Insertions into Cu−B Bonds in Copper(I) Boryl Complexes

Cited by 218 publications

References 87 publications

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross‐Coupling of Aryl Halides and Olefins

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross‐Coupling of Aryl Halides and Olefins

Reaction mechanism of palladium‐catalyzed silastannation of allenes by density functional theory

Can DFT methods correctly and efficiently predict the coordination number of copper(I) complexes? A case study

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