Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation

Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation

Bibliographic Details
Main Author: Nguyen, Hai Phuoc
Language:English
Published: University of Toledo / OhioLINK 2016
Subjects:
Chemistry
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=toledo1481314374546209
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-toledo14813143745462092021-08-03T06:39:36Z Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation Nguyen, Hai Phuoc Chemistry Iodine is common in its monovalent form, for example, CH3I. However, iodine also exists in hypervalent fashions including both ¿3-iodanes and ¿5-iodanes. Hypervalent iodine compounds are broadly used as oxidants in organic synthesis due to their mild and highly selective oxidizing properties. In addition to the oxidizing character, hypervalent iodine (III) compounds or ¿3-iodanes have been studied in reductive iodonio-Claisen rearrangement (RICR) to prepare useful alterable building blocks containing aryliodide functional group. Recently, our lab reported the synthesis of various ortho-allyliodoarenes via reductive iodonio-Claisen rearrangement from hypervalent iodine (III) compounds and allylsilane in the presence of a Lewis acid. We found that an electron-donating group at the meta-position enhanced the reactivity of the hypervalent iodine (III) compounds. We hypothesized then confirmed (by labeling studies) that the desired ortho-allyliodoarene products were formed via the [3,3]- sigma tropic rearrangement. Based on this success, we envisioned that electron-rich heteroaromatic hypervalent iodine (III) compounds would be suitable substrates for this type of rearrangement. In this report, we disclosed the synthesis of synthetically useful o-allyl iodoheteroarenes via RICR and their application in the formal synthesis of Plavix;Glycans of glycoproteins play essential roles in biological processes. While O-linked glycans are attached to serine or threonine resides, N-linked glycans attached to asparagine residue of glycoproteins. Despite the significance of the glycans, the understanding of their detailed function is often complicated by the heterogeneous glycoforms of glycoproteins. Therefore, it is important to access these glycans in chemically pure form in order to study their biological properties. For the synthesis of N-linked glycans, one of the long-standing challenges is the stereoselective construction of ß-mannopyranosides. Despite several methods developed for the synthesis of ß-mannopyranosides, in those reactions oftentimes ß-mannosides were also formed. Thus, an efficient approach which would enable the formation of sole ß-mannopyranosides is appealing. Herein, we reported the stereoselective construction of ß-mannopyranosides via anomeric O-alkylation and its application in the synthesis of N-linked oligosaccharides. 2016 English text University of Toledo / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=toledo1481314374546209 http://rave.ohiolink.edu/etdc/view?acc_num=toledo1481314374546209 unrestricted This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center.
collection NDLTD
language English
sources NDLTD
topic Chemistry
spellingShingle Chemistry
Nguyen, Hai Phuoc
Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
author Nguyen, Hai Phuoc
author_facet Nguyen, Hai Phuoc
author_sort Nguyen, Hai Phuoc
title Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
title_short Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
title_full Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
title_fullStr Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
title_full_unstemmed Reductive Iodonio-Claisen Rearrangement of Iodothiophene Diacetates withAllylsilanes and Formal Synthesis of Plavix®andStereoselective synthesis of ß-mannopyranosides via anomeric O-alkyation
title_sort reductive iodonio-claisen rearrangement of iodothiophene diacetates withallylsilanes and formal synthesis of plavix®andstereoselective synthesis of ß-mannopyranosides via anomeric o-alkyation
publisher University of Toledo / OhioLINK
publishDate 2016
url http://rave.ohiolink.edu/etdc/view?acc_num=toledo1481314374546209
work_keys_str_mv AT nguyenhaiphuoc reductiveiodonioclaisenrearrangementofiodothiophenediacetateswithallylsilanesandformalsynthesisofplavixandstereoselectivesynthesisofßmannopyranosidesviaanomericoalkyation
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