Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction
Abstract The first example of a biocatalytic [2,3]‐sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C−C bond‐forming transformation with high efficie...
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crwiley:10.1002/ange.201607278 2024-06-23T07:56:58+00:00 Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction Tyagi, Vikas Sreenilayam, Gopeekrishnan Bajaj, Priyanka Tinoco, Antonio Fasan, Rudi 2016 http://dx.doi.org/10.1002/ange.201607278 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fange.201607278 https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201607278 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Angewandte Chemie volume 128, issue 43, page 13760-13764 ISSN 0044-8249 1521-3757 journal-article 2016 crwiley https://doi.org/10.1002/ange.201607278 2024-06-06T04:20:43Z Abstract The first example of a biocatalytic [2,3]‐sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C−C bond‐forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl‐, benzyl‐, and alkyl‐substituted allylic sulfides) and α‐diazo esters. Moreover, the scope of this myoglobin‐mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active‐site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle–Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon–carbon bonds. Article in Journal/Newspaper Sperm whale Wiley Online Library Doyle ENVELOPE(-65.300,-65.300,-66.000,-66.000) Angewandte Chemie 128 43 13760 13764 |
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Open Polar |
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Wiley Online Library |
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crwiley |
language |
English |
description |
Abstract The first example of a biocatalytic [2,3]‐sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C−C bond‐forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl‐, benzyl‐, and alkyl‐substituted allylic sulfides) and α‐diazo esters. Moreover, the scope of this myoglobin‐mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active‐site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle–Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon–carbon bonds. |
format |
Article in Journal/Newspaper |
author |
Tyagi, Vikas Sreenilayam, Gopeekrishnan Bajaj, Priyanka Tinoco, Antonio Fasan, Rudi |
spellingShingle |
Tyagi, Vikas Sreenilayam, Gopeekrishnan Bajaj, Priyanka Tinoco, Antonio Fasan, Rudi Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
author_facet |
Tyagi, Vikas Sreenilayam, Gopeekrishnan Bajaj, Priyanka Tinoco, Antonio Fasan, Rudi |
author_sort |
Tyagi, Vikas |
title |
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
title_short |
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
title_full |
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
title_fullStr |
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
title_full_unstemmed |
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction |
title_sort |
biocatalytic synthesis of allylic and allenyl sulfides through a myoglobin‐catalyzed doyle–kirmse reaction |
publisher |
Wiley |
publishDate |
2016 |
url |
http://dx.doi.org/10.1002/ange.201607278 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fange.201607278 https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201607278 |
long_lat |
ENVELOPE(-65.300,-65.300,-66.000,-66.000) |
geographic |
Doyle |
geographic_facet |
Doyle |
genre |
Sperm whale |
genre_facet |
Sperm whale |
op_source |
Angewandte Chemie volume 128, issue 43, page 13760-13764 ISSN 0044-8249 1521-3757 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/ange.201607278 |
container_title |
Angewandte Chemie |
container_volume |
128 |
container_issue |
43 |
container_start_page |
13760 |
op_container_end_page |
13764 |
_version_ |
1802650387435487232 |