Towards the online computer-aided design of catalytic pockets

Falivene, Laura; Cao, Zhen; Petta, Andrea; Serra, Luigi; Poater, Albert; Oliva, Romina; Scarano, Vittorio; Cavallo, Luigi

doi:10.1038/s41557-019-0319-5

Cited by 874 publications

(812 citation statements)

References 60 publications

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“…Single-crystal X-ray diffraction structure analysis reveals that the square-planar Pd1 is highly symmetrical, rigid, and sterically encumbered, as reflected by a buried volume V Bur of 45 % ( Figure 2, right: a and b). [26] Notably, this V Bur % is less than the value (49 %) of DBB-iPr-Pd reported by Gao (Supporting Information), [24] but the DBB backbone also efficiently inhibits the rotation of axial Ipty substituents ( Figure 2, right: c). As a result, the crucial Pd-Me group is buried by the axial Ipty substituents because it is placed at the center of two wedges ( Figure 2, right: d).…”

mentioning

confidence: 64%

Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity

et al. 2020

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Branched polyolefin microstructures resulting from so‐called “chain walking” are a fascinating feature of late transition metal catalysts; however, to date it has not been demonstrated how desirable branched polyolefin microstructures can be generated thereby. We demonstrate how highly branched polyethylenes with methyl branches (220 Me/1000 C) exclusively and very high molecular weights (ca. 106 g mol−1), reaching the branch density and microstructure of commercial ethylene–propylene elastomers, can be generated from ethylene alone. At the same time, polar groups on the main chain can be generated by in‐chain incorporation of methyl acrylate. Key to this strategy is a novel rigid environment in an α‐diimine PdII catalyst with a steric constraint that allows for excessive chain walking and branching, but restricts branch formation to methyl branches, hinders chain transfer to afford a living polymerization, and inverts the regioselectivity of acrylate insertion to a 1,2‐mode.

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confidence: 64%

Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity

et al. 2020

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“…The dirhodium heterocyclic carbene 3 is by any standards sterically encumbered, taking up 63.8 % buried volume in the complex 4 (Figure ), which far exceeds that of most conventional NHC ligands . This presumably contributes to the remarkable thermal and aerobic stability of the shielded carbene donor.…”

Section: Methodsmentioning

confidence: 99%

“… Alternative representations of the steric profile of 3 . a) Steric map . b) Space‐filling with μ‐carbido shown as black.…”

Section: Methodsmentioning

confidence: 99%

A Dirhoda‐Heterocyclic Carbene

Barnett

Hill

2020

Angew Chem Int Ed

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“…Finally, to unveil the different behavior of the ruthenium catalysts bearing iodides or chlorides, the steric properties were studied by calculating the buried volume (% V Bur ) by means of the SambVca2.1 package developed by Cavallo and co-workers. [17] This computational tool was used here to describe the crowding of the metal center when the more sterically demanding iodides are included, putting the eye on a plane placed 2 away from the plane that holds the metal and both halide atoms, to better describe the interaction between the metal center and the entering olefin. In particular, quantitative comparison of the catalytic trans species with or without the Ru À S bond confirmed that iodides impose a % V Bur increase of 3.4 and 4.3 %, respectively ( Figure 6 and the Supporting Information).…”

Section: Angewandte Chemiementioning

confidence: 99%

Unprecedented Selectivity of Ruthenium Iodide Benzylidenes in Olefin Metathesis Reactions

et al. 2020

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The development of selective olefin metathesis catalysts is crucial to achieving new synthetic pathways. Herein, we show that cis‐diiodo/sulfur‐chelated ruthenium benzylidenes do not react with strained cycloalkenes and internal olefins, but can effectively catalyze metathesis reactions of terminal dienes. Surprisingly, internal olefins may partake in olefin metathesis reactions once the ruthenium methylidene intermediate has been generated. This unexpected behavior allows the facile formation of strained cis‐cyclooctene by the RCM reaction of 1,9‐undecadiene. Moreover, cis‐1,4‐polybutadiene may be transformed into small cyclic molecules, including its smallest precursor, 1,5‐cyclooctadiene, by the use of this novel sequence. Norbornenes, including the reactive dicyclopentadiene (DCPD), remain unscathed even in the presence of terminal olefin substrates as they are too bulky to approach the diiodo ruthenium methylidene. The experimental results are accompanied by thorough DFT calculations.

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Towards the online computer-aided design of catalytic pockets

Cited by 874 publications

References 60 publications

Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity

Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity

A Dirhoda‐Heterocyclic Carbene

Unprecedented Selectivity of Ruthenium Iodide Benzylidenes in Olefin Metathesis Reactions

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