Chiral calixarene and resorcinarene derivatives. Conical cavities substituted at their upper rim by two phosphito units and their use as ligands in Rh-catalysed hydroformylation

Natarajan, Nallusamy; Pierrevelcin, Marie-Christelle; Sémeril, David; Bauder, Claude; Matt, Dominique; Ramesh, Rengan

doi:10.1016/j.catcom.2018.09.020

Cited by 9 publications

(7 citation statements)

References 48 publications

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“…The catalytic solutions were analyzed by using a Varian 3900 gas chromatograph equipped with a CHROMPAK chiral fused silica Chirasil-L-Val column (25 m × 0.25 mm). (S,S)-5,17-Bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix [4]arene (1) [45] and (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′dioxyphosphanyl-oxy)calix [4]arene (2) [46] were prepared by literature procedures. 5,11,17,arene (4) [47] First, 15,16,17,18-tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene (2.500 g, 3.8 mmol) dissolved in DMF (500 mL) at 50 °C was deprotonated with NaH (60% dispersion in oil; 0.770 g, 19.3 mmol).…”

Section: Methodsmentioning

confidence: 99%

How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

Hkiri

Sémeril

2022

Organics

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Three chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1), (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (2) and (S,S)-5,11,17,23-tetra-tert-butyl-25,26-dipropoxy-27,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (3), based on conical calix[4]arene were investigated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydroamino esters. High conversions were observed after 24 h under 5 bar of hydrogen whatever the employed diphosphite, and the chiral induction increases in the order 1 < 3 < 2. This may be due to the presence of the calix[4]arene moiety, which by its presence modifies the second coordination sphere of the catalytic center. The larger steric hindrance around the rhodium atom leads to the higher enantiomeric excess.

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Section: Methodsmentioning

confidence: 99%

How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

Hkiri

Sémeril

2022

Organics

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“…Very recently, the same group synthesized two additional diphosphite ligands incorporating two (S)-BINOLate units 12a,b [29]. While 12a is derived from a calix [4]arene 1,3disubstituted at the upper ring, 12b comprises an 1,2-substituted resorcin [4]arene unit.…”

Section: Chiral Cavity-shaped Ligands Derived From Calixarenesmentioning

confidence: 99%

Cavity-shaped ligands for asymmetric metal catalysis

Kaya

Bentouhami

Pelzer

et al. 2021

Coordination Chemistry Reviews

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“…The last study was recently reported by Natarajan et al and deals with two mono‐ ( 38 and 39 ) and two bis‐phosphites ( 40 and 41 ) built on the upper rim of a calix[4]arene or a resorcin[4]arene platform (Figure ). In the optimized hydroformylation conditions (P(CO/H 2 ) = 20 bar at 50 °C for 24 h), the in situ generated catalysts obtained by mixing [Rh(acac)(CO) 2 ] and excess of ligands (10 equiv.…”

Section: Rhodium‐catalyzed Styrene Hydroformylationmentioning

confidence: 99%

Styrene Hydroformylation with Cavity‐Shaped Ligands

Bauder

Sémeril

2019

Eur J Inorg Chem

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The goal of this review is to give an up-to-date overview of phosphorus(III)-functionalized calixarenes, resorcinar-Scheme 1. Hydroformylation of α-olefins with side reactions. [a] David Sémeril is a "Chargé de recherche" within the CNRS. After a PhD in catalysis under the supervision of Dr. C. Bruneau and Prof. P. H. Dixneuf in Rennes, he carried out postdoctoral studies in Pisa on polymer chemistry with Prof. F. Ciardelli, then in Florence with Dr. C. Bianchini, where he developed several active polymerization catalysts based on conformationally restricted ligands. He joined the CNRS in 2003 within the laboratory of Dr. D. Matt in Strasbourg, where he has actively developed a research program on the application of ligands derived from molecular cavities (calixarenes and resorcinarenes) in homogeneous catalysis. He passed his habilitation qualification in 2008 and his most remarkable recent results concern highly selective hydroformylation catalysts and efficient supramolecular catalysts, all based on macrocyclic skeletons. He was awarded the Gineste Prize (University of 4951 enes and cyclodextrins as ligands for rhodium-and platinumcatalyzed styrene hydroformylation. Scheme 2. Equilibrium between rhodium species. Scheme 3. Catalytic cycle for styrene hydroformylation.Figure 1. Generic calix[n]arenes (A), cyclodextrins (α-CD and -CD) (B), resorcin[4]arenes (C), and resorcin[4]arene-cavitands (D).

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Chiral calixarene and resorcinarene derivatives. Conical cavities substituted at their upper rim by two phosphito units and their use as ligands in Rh-catalysed hydroformylation

Cited by 9 publications

References 48 publications

How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

Cavity-shaped ligands for asymmetric metal catalysis

Styrene Hydroformylation with Cavity‐Shaped Ligands

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