1,1,2-Trifunctionalization of terminal alkynes by imine/borane frustrated Lewis pairs

Ullah, Aziz; Chen, Guo-Qiang

doi:10.1039/d2qo00640e

Cited by 6 publications

(2 citation statements)

References 63 publications

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“…Binding to the electrophilic gold( i ) center lowers the barrier for deprotonation by the basic Rh center to 15.3 kcal mol −1 , 15 in a way that is resemblant of conventional FLPs. 16 However, this reaction is thermoneutral relative to the fragments, but overall endergonic relative to 4a Tripp . We also computed these fragments independently to ensure translational entropy was not responsible for the endergonicity ( Fig.…”

Section: Resultsmentioning

confidence: 97%

Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

et al. 2023

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Section: Resultsmentioning

confidence: 97%

Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

et al. 2023

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“…A very interesting result was reported by Repo et al in 2016. 60 In 2022, Ullah and Chen 61 reported the reaction of imines and boranes in the presence of alkynes at 80 °C which proceeded via FLP deprotonation. However, the resulting alkynyl borate reacts further with the iminium cation to deliver the alkynyl group to the electrophilic carbon.…”

Section: Nitrogen Donorsmentioning

confidence: 99%

Frustrated Lewis pair chemistry of alkynes

Guo,

Yan,

Stephan

2024

Org. Chem. Front.

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Density functional theory study on frustrated Lewis pairs catalyzed C‐H activation of heteroarenes: Mechanism variation tuning by electronic effect

Shao,

Xiao,

Wang

et al. 2024

J of Physical Organic Chem

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Unreactive C‐H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C‐H bond activation of 1‐methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well‐understood. In this study, an assortment of P‐B type FLPs with different electronic characteristic was employed to study the catalyzed C‐H bond activation of 1‐methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C‐H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C‐H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron‐donating substituents (FLP1, FLP2, and FLP3) catalyzed the C‐H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing ‐P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four‐membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C‐H bond activation.

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1,1,2-Trifunctionalization of terminal alkynes by imine/borane frustrated Lewis pairs

Abstract: A metal-free one-pot 1,1,2-trifunctionalization of terminal alkynes with imines and boranes is reported. The reaction proceeds via FLP deprotonation and alkynyl borate 1,2-migration sequence, with no need of any organolithium...

Cited by 6 publications

References 63 publications

Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

Polarized Au(i)/Rh(i) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation

Frustrated Lewis pair chemistry of alkynes

Density functional theory study on frustrated Lewis pairs catalyzed C‐H activation of heteroarenes: Mechanism variation tuning by electronic effect

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