Sulfoxidation inside a C3-vanadium(V) bowl-shaped catalyst

Dawei Zhang; Jean Pierre Dutasta; Veronique Dufaud; Laure Guy; Alexandre Martinez

doi:10.1021/acscatal.7b01886

Sulfoxidation inside a C₃-vanadium(V) bowl-shaped catalyst

Dawei Zhang, Jean Pierre Dutasta, Veronique Dufaud, Laure Guy, Alexandre Martinez

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 10⁵ was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.

Original language	English
Pages (from-to)	7340-7345
Number of pages	6
Journal	ACS Catalysis
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.7b01886
State	Published - 6 Oct 2017
Externally published	Yes

Keywords

Chiral pocket
Enantioselectivity
High TON
Oxido-vanadium complex
Sulfoxidation
Supramolecular catalysis

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10.1021/acscatal.7b01886

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title = "Sulfoxidation inside a C3-vanadium(V) bowl-shaped catalyst",

abstract = "The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 105 was reached in combination with a good selectivity (more than 90\%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.",

keywords = "Chiral pocket, Enantioselectivity, High TON, Oxido-vanadium complex, Sulfoxidation, Supramolecular catalysis",

author = "Dawei Zhang and Dutasta, \{Jean Pierre\} and Veronique Dufaud and Laure Guy and Alexandre Martinez",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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day = "6",

doi = "10.1021/acscatal.7b01886",

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T1 - Sulfoxidation inside a C3-vanadium(V) bowl-shaped catalyst

AU - Zhang, Dawei

AU - Dutasta, Jean Pierre

AU - Dufaud, Veronique

AU - Guy, Laure

AU - Martinez, Alexandre

PY - 2017/10/6

Y1 - 2017/10/6

N2 - The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 105 was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.

AB - The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 105 was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.

KW - Chiral pocket

KW - Enantioselectivity

KW - High TON

KW - Oxido-vanadium complex

KW - Sulfoxidation

KW - Supramolecular catalysis

UR - https://www.scopus.com/pages/publications/85032748962

U2 - 10.1021/acscatal.7b01886

DO - 10.1021/acscatal.7b01886

M3 - 文章

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SN - 2155-5435

VL - 7

SP - 7340

EP - 7345

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

Sulfoxidation inside a C₃-vanadium(V) bowl-shaped catalyst

Abstract

Keywords

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