Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes
An iodine-mediated hydration reaction of alkynes serves as a green alternative to metal-catalyzed procedures. Previous work has shown that this method works well with terminal alkynes on keto-functionalized scaffolds, including 1,3-dicarbonyls and their heteroatom analogues. It was hypothesized that...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Beilstein-Institut
2019-11-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.15.265 |
| _version_ | 1818620051768475648 |
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| author | Zachary Lee Brandon R. Jones Nyochembeng Nkengbeza Michael Phillips Kayla Valentine Alexis Stewart Brandon Sellers Nicholas Shuber Karelle S. Aiken |
| author_facet | Zachary Lee Brandon R. Jones Nyochembeng Nkengbeza Michael Phillips Kayla Valentine Alexis Stewart Brandon Sellers Nicholas Shuber Karelle S. Aiken |
| author_sort | Zachary Lee |
| collection | DOAJ |
| description | An iodine-mediated hydration reaction of alkynes serves as a green alternative to metal-catalyzed procedures. Previous work has shown that this method works well with terminal alkynes on keto-functionalized scaffolds, including 1,3-dicarbonyls and their heteroatom analogues. It was hypothesized that the reaction proceeds through a 5-exo-dig neighboring group participation (NGP) cyclization and an α-iodo intermediate. The work described herein probes the existence of the intermediate through NMR investigations and explores the scope of the hydration process with internal alkynes. The NMR experiments confirm the existence of the α-iodo intermediate, and methodology studies demonstrate that alkyl-capped, asymmetric, internal alkynes undergo a regiospecific hydration, also via the 5-exo-dig NGP pathway. |
| first_indexed | 2024-12-16T17:47:14Z |
| format | Article |
| id | doaj.art-fe992150c3d24daa9f47706293b8fb60 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-16T17:47:14Z |
| publishDate | 2019-11-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-fe992150c3d24daa9f47706293b8fb602022-12-21T22:22:26ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972019-11-011512747275210.3762/bjoc.15.2651860-5397-15-265Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynesZachary Lee0Brandon R. Jones1Nyochembeng Nkengbeza2Michael Phillips3Kayla Valentine4Alexis Stewart5Brandon Sellers6Nicholas Shuber7Karelle S. Aiken8Chemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAChemistry & Biochemistry, Georgia Southern University, PO Box 8064, Statesboro, GA 30460, USAAn iodine-mediated hydration reaction of alkynes serves as a green alternative to metal-catalyzed procedures. Previous work has shown that this method works well with terminal alkynes on keto-functionalized scaffolds, including 1,3-dicarbonyls and their heteroatom analogues. It was hypothesized that the reaction proceeds through a 5-exo-dig neighboring group participation (NGP) cyclization and an α-iodo intermediate. The work described herein probes the existence of the intermediate through NMR investigations and explores the scope of the hydration process with internal alkynes. The NMR experiments confirm the existence of the α-iodo intermediate, and methodology studies demonstrate that alkyl-capped, asymmetric, internal alkynes undergo a regiospecific hydration, also via the 5-exo-dig NGP pathway.https://doi.org/10.3762/bjoc.15.265α-iodo intermediateinternal alkyneiodine-mediated hydrationneighboring group participationregiospecific hydration |
| spellingShingle | Zachary Lee Brandon R. Jones Nyochembeng Nkengbeza Michael Phillips Kayla Valentine Alexis Stewart Brandon Sellers Nicholas Shuber Karelle S. Aiken Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes Beilstein Journal of Organic Chemistry α-iodo intermediate internal alkyne iodine-mediated hydration neighboring group participation regiospecific hydration |
| title | Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes |
| title_full | Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes |
| title_fullStr | Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes |
| title_full_unstemmed | Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes |
| title_short | Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes |
| title_sort | iodine mediated hydration of alkynes on keto functionalized scaffolds mechanistic insight and the regiospecific hydration of internal alkynes |
| topic | α-iodo intermediate internal alkyne iodine-mediated hydration neighboring group participation regiospecific hydration |
| url | https://doi.org/10.3762/bjoc.15.265 |
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