Highly Selective Radical Monoreduction of Dihalides Confined to a Dynamic Supramolecular Host

Petroselli, Manuel; Rebek, Julius; Yu, Yang

doi:10.1002/chem.202004953

Cited by 4 publications

(4 citation statements)

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“… [53] Here, in order to give further information of the effects of confinement on fast radical reactions (k≥10 3 m −1 s −1 ), the reduction of alkyl dihalide guests with trialkylsilanes (R 3 SiH) was performed in a water‐soluble metallo‐cavitand H6 − 2Pd (Figure 14 ). [54] Excellent conversion (>94 %) and high selectivity (>95 %) for the mono‐reduced products were obtained for both primary and secondary dihalides, even when 2 or 3 equivalents of the reducing agents were used. In bulk solution, only low selectivity could be observed.…”

Section: Reactivity In Water‐soluble Deep Cavitandsmentioning

confidence: 95%

Recent Advances in the Applications of Water‐soluble Resorcinarene‐based Deep Cavitands

et al. 2022

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We review here the use of container molecules known as cavitands for performing organic reactions in water. Central to these endeavors are binding forces found in water, and among the strongest of these is the hydrophobic effect. We describe how the hydrophobic effect can be used to drive organic molecule guests into the confined space of cavitand hosts. Other forces participating in guest binding include cationÀ π interactions, chalcogen bonding and even hydrogen bonding to water involved in the host structure. The reactions of guests take advantage of their contortions in the limited space of the cavitands which enhance macrocyclic and site-selective processes. The cavitands are applied to the removal of organic pollutants from water and to the separation of isomeric guests. Progress is described on maneuvering the containers from stoichiometric participation to roles as catalysts.

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Section: Reactivity In Water‐soluble Deep Cavitandsmentioning

confidence: 95%

Recent Advances in the Applications of Water‐soluble Resorcinarene‐based Deep Cavitands

et al. 2022

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“…This work represented the first example of supramolecular containers applied for a radical reaction involving external radical initiators with dynamic hosts. Later, this group reported another highly site-selective radical monoreduction of dihalides by trialkylsilanes (R 3 SiH) using the similar strategy [ 63 ].…”

Section: Reviewmentioning

confidence: 99%

Site-selective reactions mediated by molecular containers

Wang¹,

Yu²

2022

Beilstein J. Org. Chem.

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In this review, we summarize various site-selective reactions mediated by molecular containers. The emphasis is on those reactions that give different product distributions on the potential reactive sites inside the containers than they do outside, free in solution. Specific cases include site-selective cycloaddition and addition of arenes, reduction of epoxides, α,β-unsaturated aldehydes, azides, halides and alkenes, oxidation of remote C–H bonds and alkenes, and substitution reactions involving ring-opening cyclization of epoxides, nucleophilic substitution of allylic chlorides, and hydrolysis reactions. The product selectivity is interpreted as the consequence of the space shape and environment inside the container. The containers include supramolecular structures self-assembled through metal/ligand interactions or hydrogen bonding and open-ended covalent structures such as cyclodextrins and cavitands. Challenges and prospects for the future are also provided.

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“…This highlight will focus on supramolecular container-mediated organic radical reactions, including our recent applications. 13,14…”

Section: Introductionmentioning

confidence: 99%

“…In a subsequent work, our group reported a highly selective radical monoreduction of dihalides with cavitands, using (TMS) 3 SiH as the radical initiator. 14…”

Section: Introductionmentioning

confidence: 99%