Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
The reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hyper...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2018-05-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.14.91 |
| _version_ | 1818327366937608192 |
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| author | Cyrus Mowdawalla Faiz Ahmed Tian Li Kiet Pham Loma Dave Grace Kim I. F. Dempsey Hyatt |
| author_facet | Cyrus Mowdawalla Faiz Ahmed Tian Li Kiet Pham Loma Dave Grace Kim I. F. Dempsey Hyatt |
| author_sort | Cyrus Mowdawalla |
| collection | DOAJ |
| description | The reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hypervalent iodine’s metal-like properties it was concluded that a transmetallation mechanism could be occurring with metalloid groups such as silicon and boron. Hypervalent iodine reagents such as Zefirov’s reagent, cyclic iodonium reagents, iodosobenzene/BF3, and PhI(OAc)2/BF3 or triflate-based activators were tested. A desirable facet of the reported reaction is that iodine(I) is incorporated into the product thus providing greater atom economy and a valuable functional group handle for further transformations. The altering of the RICR’s ortho-selectivity to form para-selective products with benzyl hypervalent iodine intermediates suggests a mechanism that involves hypervalent iodine-guided electrophilic substitution (HIGES). |
| first_indexed | 2024-12-13T12:15:08Z |
| format | Article |
| id | doaj.art-ed1eeedb70b944379894e023c2654046 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-13T12:15:08Z |
| publishDate | 2018-05-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-ed1eeedb70b944379894e023c26540462022-12-21T23:46:45ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972018-05-011411039104510.3762/bjoc.14.911860-5397-14-91Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groupsCyrus Mowdawalla0Faiz Ahmed1Tian Li2Kiet Pham3Loma Dave4Grace Kim5I. F. Dempsey Hyatt6Department of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USADepartment of Chemistry and Biochemistry, Adelphi University, 1 South Ave., Garden City, NY, 11530, USAThe reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hypervalent iodine’s metal-like properties it was concluded that a transmetallation mechanism could be occurring with metalloid groups such as silicon and boron. Hypervalent iodine reagents such as Zefirov’s reagent, cyclic iodonium reagents, iodosobenzene/BF3, and PhI(OAc)2/BF3 or triflate-based activators were tested. A desirable facet of the reported reaction is that iodine(I) is incorporated into the product thus providing greater atom economy and a valuable functional group handle for further transformations. The altering of the RICR’s ortho-selectivity to form para-selective products with benzyl hypervalent iodine intermediates suggests a mechanism that involves hypervalent iodine-guided electrophilic substitution (HIGES).https://doi.org/10.3762/bjoc.14.91electrophilic aromatic substitutionhypernucleofugalityhypervalent iodineiodonio-Claisentransmetallation |
| spellingShingle | Cyrus Mowdawalla Faiz Ahmed Tian Li Kiet Pham Loma Dave Grace Kim I. F. Dempsey Hyatt Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups Beilstein Journal of Organic Chemistry electrophilic aromatic substitution hypernucleofugality hypervalent iodine iodonio-Claisen transmetallation |
| title | Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups |
| title_full | Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups |
| title_fullStr | Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups |
| title_full_unstemmed | Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups |
| title_short | Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups |
| title_sort | hypervalent iodine guided electrophilic substitution para selective substitution across aryl iodonium compounds with benzyl groups |
| topic | electrophilic aromatic substitution hypernucleofugality hypervalent iodine iodonio-Claisen transmetallation |
| url | https://doi.org/10.3762/bjoc.14.91 |
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