Publicação
UNLOCKING THE REACTIVITY OF HYPERVALENT IODINE REAGENTS EXPLORING NEW SYNTHETIC APPROACHES WITH IODINE (III) CHEMISTRY
| Resumo: | Hypervalent iodine reagents (HIRs) represent a diverse and promising class of compounds that have attracted significant attention in recent years. Primarily recognized for their role as oxidizing agents they have emerged as bench-stable and sustainable alternatives to more traditional reagents, particularly as electrophilic group-transfer reagents. This thesis covers my research on HIRs, particularly the efforts to expand their reactivity profile. Thus, a new method for the preparation of sulfones was investigated. This method relied on combining the reactivity of in situ generated HIR bearing a sulfonyl group with the chemistry of organometallic reagents, particularly organozinc pivalates. Several sulfones, both aliphatic and aromatic were prepared (12 reported in this document) in moderate to good yields (up to 84%). In parallel, four HIR bearing a primary amine were prepared and their reactivity investigated in different reactions: using zinc pivalate reagents to produce primary amine/amides; using amines as nucleophiles to prepare hydrazines; and also, alkenes to produce amines. The reaction with the zinc pivalate reagents afforded the corresponding amines (10 reported in this document) in good yields (up to 97%). These amines were generated in situ and subsequently converted to their corresponding N-benzoyl derivatives. Although the preliminary results are encouraging, further work is required to improve yields and broaden functional group tolerance. While the reaction with the zinc pivalates afforded the desired amines, the studies undertaken with the nucleophilic amines did not deliver the corresponding hydrazines. The project also explored the photocatalytic functionalization of functionalized alkenes using the HIRs, as a greener strategy for investigating radical pathways. Although this direction did not yield impactful results further experiments are ongoing. |
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| Autores principais: | Rocha, Gabriel Gregório Moreira |
| Assunto: | Electrophilic Amination Hypervalent Iodine Reagents Umpolung Photocatalysis Sulfones Primary Amines |
| Ano: | 2025 |
| País: | Portugal |
| Tipo de documento: | dissertação de mestrado |
| Tipo de acesso: | acesso embargado |
| Instituição associada: | Universidade Nova de Lisboa |
| Idioma: | inglês |
| Origem: | Repositório Institucional da UNL |
| Resumo: | Hypervalent iodine reagents (HIRs) represent a diverse and promising class of compounds that have attracted significant attention in recent years. Primarily recognized for their role as oxidizing agents they have emerged as bench-stable and sustainable alternatives to more traditional reagents, particularly as electrophilic group-transfer reagents. This thesis covers my research on HIRs, particularly the efforts to expand their reactivity profile. Thus, a new method for the preparation of sulfones was investigated. This method relied on combining the reactivity of in situ generated HIR bearing a sulfonyl group with the chemistry of organometallic reagents, particularly organozinc pivalates. Several sulfones, both aliphatic and aromatic were prepared (12 reported in this document) in moderate to good yields (up to 84%). In parallel, four HIR bearing a primary amine were prepared and their reactivity investigated in different reactions: using zinc pivalate reagents to produce primary amine/amides; using amines as nucleophiles to prepare hydrazines; and also, alkenes to produce amines. The reaction with the zinc pivalate reagents afforded the corresponding amines (10 reported in this document) in good yields (up to 97%). These amines were generated in situ and subsequently converted to their corresponding N-benzoyl derivatives. Although the preliminary results are encouraging, further work is required to improve yields and broaden functional group tolerance. While the reaction with the zinc pivalates afforded the desired amines, the studies undertaken with the nucleophilic amines did not deliver the corresponding hydrazines. The project also explored the photocatalytic functionalization of functionalized alkenes using the HIRs, as a greener strategy for investigating radical pathways. Although this direction did not yield impactful results further experiments are ongoing. |
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