Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination
Abstract Herein, DFT studies corroborating experimental results revealed that the shortest intramolecular hydrogen bonding distance of cis/trans‐oxaphosphetane (OPA) oxygen with the CH‐hydrogen of a triphenylphosphine phenyl ring provides good evidence for the attained olefin Z/E‐selectivity in Witt...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-03-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.202300171 |
| _version_ | 1797267950357446656 |
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| author | Dr. Kukkamudi Sreenivas Dr. Chintada Nageswara Rao Dr. Faiz Ahmed Khan |
| author_facet | Dr. Kukkamudi Sreenivas Dr. Chintada Nageswara Rao Dr. Faiz Ahmed Khan |
| author_sort | Dr. Kukkamudi Sreenivas |
| collection | DOAJ |
| description | Abstract Herein, DFT studies corroborating experimental results revealed that the shortest intramolecular hydrogen bonding distance of cis/trans‐oxaphosphetane (OPA) oxygen with the CH‐hydrogen of a triphenylphosphine phenyl ring provides good evidence for the attained olefin Z/E‐selectivity in Wittig olefination of the studied examples. 2‐Nitrobenzaldehyde, 3‐nitrobenzaldehyde, 2‐nitro‐3‐bromobenzaldehyde, 2‐nitro‐5‐bromobenzaldehyde and 2‐nitro‐5‐arylbenzaldehydes provided Z‐nitrostilbenes with (2‐chloro‐4‐hydroxy‐3‐methoxy‐5‐(methoxycarbonyl)benzyl) triphenylphosphonium chloride as the major products. However, 4‐nitrobenzaldehyde and 2‐nitro‐6‐bromobenzaldehydes furnished E‐nitrostilbenes as the major products in high yields. Furthermore, the DFT computed intramolecular CH1/CH2‐hydrogen bond distances with Cl/NO2 of selected stilbene derivatives were in good agreement with intramolecular hydrogen bond distances measured from single‐crystal X‐ray diffraction measurements. |
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| format | Article |
| id | doaj.art-72c5364786b84bdbb9072ae77a144d6f |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-04-25T01:24:43Z |
| publishDate | 2024-03-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-72c5364786b84bdbb9072ae77a144d6f2024-03-09T04:02:58ZengWiley-VCHChemistryOpen2191-13632024-03-01133n/an/a10.1002/open.202300171Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig OlefinationDr. Kukkamudi Sreenivas0Dr. Chintada Nageswara Rao1Dr. Faiz Ahmed Khan2Department of Chemistry Indian Institute of Technology Hyderabad Kandi Sangareddy Telangana 502 285 IndiaDepartment of Drug Discovery and Biomedical Sciences, College of Pharmacy University of South Carolina Columbia SC-29208 USADepartment of Chemistry Indian Institute of Technology Hyderabad, Kandi Sangareddy Telangana 502 285 IndiaAbstract Herein, DFT studies corroborating experimental results revealed that the shortest intramolecular hydrogen bonding distance of cis/trans‐oxaphosphetane (OPA) oxygen with the CH‐hydrogen of a triphenylphosphine phenyl ring provides good evidence for the attained olefin Z/E‐selectivity in Wittig olefination of the studied examples. 2‐Nitrobenzaldehyde, 3‐nitrobenzaldehyde, 2‐nitro‐3‐bromobenzaldehyde, 2‐nitro‐5‐bromobenzaldehyde and 2‐nitro‐5‐arylbenzaldehydes provided Z‐nitrostilbenes with (2‐chloro‐4‐hydroxy‐3‐methoxy‐5‐(methoxycarbonyl)benzyl) triphenylphosphonium chloride as the major products. However, 4‐nitrobenzaldehyde and 2‐nitro‐6‐bromobenzaldehydes furnished E‐nitrostilbenes as the major products in high yields. Furthermore, the DFT computed intramolecular CH1/CH2‐hydrogen bond distances with Cl/NO2 of selected stilbene derivatives were in good agreement with intramolecular hydrogen bond distances measured from single‐crystal X‐ray diffraction measurements.https://doi.org/10.1002/open.202300171benzylphosphonium saltsWittig olefinationhydrogen bondingnitrostilbenes2-arylindoles |
| spellingShingle | Dr. Kukkamudi Sreenivas Dr. Chintada Nageswara Rao Dr. Faiz Ahmed Khan Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination ChemistryOpen benzylphosphonium salts Wittig olefination hydrogen bonding nitrostilbenes 2-arylindoles |
| title | Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination |
| title_full | Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination |
| title_fullStr | Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination |
| title_full_unstemmed | Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination |
| title_short | Intramolecular CH‐Hydrogen Bonding During the Dissociation of the Oxaphosphetane Intermediate Facilitates Z/E‐Selectivity in Wittig Olefination |
| title_sort | intramolecular ch hydrogen bonding during the dissociation of the oxaphosphetane intermediate facilitates z e selectivity in wittig olefination |
| topic | benzylphosphonium salts Wittig olefination hydrogen bonding nitrostilbenes 2-arylindoles |
| url | https://doi.org/10.1002/open.202300171 |
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