Regiodivergent hydroallylation of 1,3-diynes controlled by nickel and palladium catalysts

Zhang, Sheng; Zhang, Hao; Zhan, Zhuang‐Ping

doi:10.1039/d1qo01928g

Cited by 2 publications

(1 citation statement)

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“…Bidentate phosphorus ligands were selected as model compounds because they are in high demand in organic synthesis [86][87][88][89] and catalysis. [52][53][54][55][56][57][90][91][92] A representative example of the use of the DPPE-d 4 complex in the study of the reaction mechanism is highlighted elsewhere. 93 Potentially, both 13 Cand D-labeled phosphorus ligands can be used for precise identification of structures of organic molecules, since a unique combination of multiplets appears in 13 C-and 31 P-NMR and mass change is observable in the HRMS spectra.…”

Section: Introductionmentioning

confidence: 99%

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

et al. 2023

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Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses

Liu

et al. 2023

J. Org. Chem.

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Density functional theory calculations were employed to investigate the Pd-catalyzed regio-selective hydroallylations of alkynes with allylborons: cooperation of Cu(OAc) 2 and dppe resulting in 1,4-dienes while combination of AdCO 2 H and PCy 3 leading to 1,5-dienes. A unified rationalization mechanism called "Lewis-acid−base-interaction promoted deprotonation/3,3-rearrangement" was proposed. Compared with the commonly reported metathesis pathway to only afford the metal-allyl intermediate, in the newly established mechanism, an additional Brønsted acid (as an initiator of the Pd 0 oxidative addition) is generated by the interaction of the allylboron (Lewis acid) B atom with the n BuOH (Lewis base) O atom, and subsequent 3,3rearrangement ensures the thermodynamic feasibility of the reaction. In addition, it was found that excess Cu(OAc) 2 plays two potential roles in the oxidative addition/alkyne insertion: (i) the participation of one AcO − of Cu(OAc) 2 ensures a large orbital overlap between the migrating H and Pd atoms, facilitating the formal AcO−H cleavage and (ii) the extra (OAc) 2 Cu•••O(carboxyl) σ-coordination indirectly contributes to the (Me)C�C(Ph) insertion into the Pd−H bond. Further analysis showed that the origin of the regioselectivity is closely related to the employed phosphorus ligand. These revealed results, which have been overlooked in the previous documents, would aid the development of new related catalytic reactions.

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Regiodivergent hydroallylation of 1,3-diynes controlled by nickel and palladium catalysts

Abstract: A highly efficient hydroallylation reaction of 1,3-diynes with allylborons was developed, with the regioselectivity governed primarily by the appropriate choice of the metal. A series of unsymmetrical and symmetrical 1,3-diynes...

Cited by 2 publications

References 31 publications

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses

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Regiodivergent hydroallylation of 1,3-diynes controlled by nickel and palladium catalysts

Abstract: A highly efficient hydroallylation reaction of 1,3-diynes with allylborons was developed, with the regioselectivity governed primarily by the appropriate choice of the metal. A series of unsymmetrical and symmetrical 1,3-diynes...

Cited by 2 publications

References 31 publications

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and13C-labeled bidentate phosphorus ligands and metal complexes

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and13C-labeled bidentate phosphorus ligands and metal complexes

Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses

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Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and¹³C-labeled bidentate phosphorus ligands and metal complexes