Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase
Abstract A p ‐nitrophenylphosphonate palladium pincer was synthesized and selectively inserted by irreversible attachment on the catalytic serine of different commercial lipases with good to excellent yields in most cases. Among all, lipase from Candida antarctica B (CAL‐B) was the best modified enz...
Published in: | Advanced Synthesis & Catalysis |
---|---|
Main Authors: | , , , , , |
Other Authors: | , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
Wiley
2015
|
Subjects: | |
Online Access: | http://dx.doi.org/10.1002/adsc.201500014 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201500014 https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201500014 |
id |
crwiley:10.1002/adsc.201500014 |
---|---|
record_format |
openpolar |
spelling |
crwiley:10.1002/adsc.201500014 2024-09-30T14:24:43+00:00 Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase Filice, Marco Romero, Oscar Aires, Antonio Guisan, Jose M. Rumbero, Angel Palomo, Jose M. CSIC ESF (European Social Fund) CONICYT Programa Bicentenario Becas-Chile 2015 http://dx.doi.org/10.1002/adsc.201500014 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201500014 https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201500014 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Advanced Synthesis & Catalysis volume 357, issue 12, page 2687-2696 ISSN 1615-4150 1615-4169 journal-article 2015 crwiley https://doi.org/10.1002/adsc.201500014 2024-09-17T04:49:35Z Abstract A p ‐nitrophenylphosphonate palladium pincer was synthesized and selectively inserted by irreversible attachment on the catalytic serine of different commercial lipases with good to excellent yields in most cases. Among all, lipase from Candida antarctica B (CAL‐B) was the best modified enzyme. The artificial metalloenzyme CAL‐B‐palladium (Pd) catalyst was subsequently immobilized on different supports and by different orienting strategies. The catalytic properties of the immobilized hybrid catalysts were then evaluated in two sets of Heck cross‐coupling reactions under different conditions. In the first reaction between iodobenzene and ethyl acrylate, the covalent immobilized CAL‐B‐Pd catalyst resulted to be the best one exhibiting quantitative production of the Heck product at 70 °C in dimethylformamide (DMF) with 25% water and particularly in pure DMF, where the soluble Pd pincer was completely inactive. A post‐immobilization engineering of catalyst surface by its hydrophobization enhanced the activity. The selectivity properties of the best hybrid catalyst were then assessed in the asymmetric Heck cross‐coupling reaction between iodobenzene and 2,3‐dihydrofuran retrieving excellent results in terms of stereo‐ and enantioselectivity. magnified image Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library Advanced Synthesis & Catalysis 357 12 2687 2696 |
institution |
Open Polar |
collection |
Wiley Online Library |
op_collection_id |
crwiley |
language |
English |
description |
Abstract A p ‐nitrophenylphosphonate palladium pincer was synthesized and selectively inserted by irreversible attachment on the catalytic serine of different commercial lipases with good to excellent yields in most cases. Among all, lipase from Candida antarctica B (CAL‐B) was the best modified enzyme. The artificial metalloenzyme CAL‐B‐palladium (Pd) catalyst was subsequently immobilized on different supports and by different orienting strategies. The catalytic properties of the immobilized hybrid catalysts were then evaluated in two sets of Heck cross‐coupling reactions under different conditions. In the first reaction between iodobenzene and ethyl acrylate, the covalent immobilized CAL‐B‐Pd catalyst resulted to be the best one exhibiting quantitative production of the Heck product at 70 °C in dimethylformamide (DMF) with 25% water and particularly in pure DMF, where the soluble Pd pincer was completely inactive. A post‐immobilization engineering of catalyst surface by its hydrophobization enhanced the activity. The selectivity properties of the best hybrid catalyst were then assessed in the asymmetric Heck cross‐coupling reaction between iodobenzene and 2,3‐dihydrofuran retrieving excellent results in terms of stereo‐ and enantioselectivity. magnified image |
author2 |
CSIC ESF (European Social Fund) CONICYT Programa Bicentenario Becas-Chile |
format |
Article in Journal/Newspaper |
author |
Filice, Marco Romero, Oscar Aires, Antonio Guisan, Jose M. Rumbero, Angel Palomo, Jose M. |
spellingShingle |
Filice, Marco Romero, Oscar Aires, Antonio Guisan, Jose M. Rumbero, Angel Palomo, Jose M. Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
author_facet |
Filice, Marco Romero, Oscar Aires, Antonio Guisan, Jose M. Rumbero, Angel Palomo, Jose M. |
author_sort |
Filice, Marco |
title |
Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
title_short |
Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
title_full |
Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
title_fullStr |
Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
title_full_unstemmed |
Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase |
title_sort |
preparation of an immobilized lipase‐palladium artificial metalloenzyme as catalyst in the heck reaction: role of the solid phase |
publisher |
Wiley |
publishDate |
2015 |
url |
http://dx.doi.org/10.1002/adsc.201500014 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201500014 https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201500014 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
Advanced Synthesis & Catalysis volume 357, issue 12, page 2687-2696 ISSN 1615-4150 1615-4169 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/adsc.201500014 |
container_title |
Advanced Synthesis & Catalysis |
container_volume |
357 |
container_issue |
12 |
container_start_page |
2687 |
op_container_end_page |
2696 |
_version_ |
1811642017478868992 |