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

NWIPB OpenIR

	Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses
	Liu, Lingjun; Liu, Yuxia; Wu, Qiao; Zhao, Xufang; Li, Yulin; Chen, Guang; Bi, Siwei
	2023
发表期刊	JOURNAL OF ORGANIC CHEMISTRY
卷号	88 期号:7 页码:4536
摘要	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 PCy3 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 Bri nsted acid (as an initiator of the Pd-0 oxidative addition) is generated by the interaction of the allylboron (Lewis acid) B atom with the nBuOH (Lewis base) O atom, and subsequent 3,3 rearrangement 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 center dot center dot center dot O(carboxyl) sigma-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.
收录类别	SCIE
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/61672
专题	中国科学院西北高原生物研究所
推荐引用方式 GB/T 7714	Liu, Lingjun,Liu, Yuxia,Wu, Qiao,et al. Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses[J]. JOURNAL OF ORGANIC CHEMISTRY,2023,88(7):4536.
APA	Liu, Lingjun.,Liu, Yuxia.,Wu, Qiao.,Zhao, Xufang.,Li, Yulin.,...&Bi, Siwei.(2023).Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses.JOURNAL OF ORGANIC CHEMISTRY,88(7),4536.
MLA	Liu, Lingjun,et al."Mechanistic Investigation into the Regio-Controllable Hydroallylations of Alkynes with Allylborons under Pd-Based Synergetic Catalyses".JOURNAL OF ORGANIC CHEMISTRY 88.7(2023):4536.