Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/142580
Title: Carbene-catalyzed dynamic kinetic resolution for asymmetric access to phthalidyl esters and benzofuranone derivatives
Authors: Majhi, Pankaj Kumar
Keywords: Science::Chemistry
Issue Date: 2020
Publisher: Nanyang Technological University
Source: Majhi, P. K. (2020). Carbene-catalyzed dynamic kinetic resolution for asymmetric access to phthalidyl esters and benzofuranone derivatives. Doctoral thesis, Nanyang Technological University, Singapore.
Abstract: In this thesis, we have demonstrated two dynamic kinetic resolution strategies enabled by N-heterocyclic carbene. Firstly, asymmetric acylation of hydroxyphthalides through N-heterocyclic carbene catalyzed dynamic kinetic resolution approach has been achieved. In addition, enantioselective modification of hydroxyphthalides containing natural products has also been achieved utilizing this DKR process. Secondly, enantioselective synthesis of 3,3'-disubstituted benzofuran-2(3H)-one derivatives bearing vicinal quaternary stereogenic centers, enabled by N-heterocyclic carbene catalyzed dynamic kinetic resolution process, has been developed. We anticipated that these methodologies can play a vital role in the synthesis of medicinally important molecules and natural products. In chapter 1, a brief introduction of dynamic kinetic resolution approach and different modes of reactions enabled by NHC catalysis have been demonstrated. N-heterocyclic carbene-catalyzed kinetic resolution and dynamic kinetic resolution have also been introduced in this chapter. In chapter 2, enantioselective acylation of hydroxyphthalides via NHC-catalyzed dynamic kinetic resolution approach has been discussed. Phthalidyl esters were achieved with high enantioselectivities and high yields (up to 99:1 e.r. and up to 96% yield). Moreover, asymmetric modification of natural products that contained hydroxyphthalide units, such as Corollosporine and Fimbricalyxlactone C, have also been demonstrated. In chapter 3, asymmetric synthesis of 3,3'-disubstituted benzofuran-2(3H)-one derivatives bearing vicinal quaternary stereogenic centers, enabled by N-heterocyclic carbene through dynamic kinetic resolution approach has been introduced. The reaction undergoes via intermolecular reversible aldol reaction followed by acylation between benzofuranyl carbonate and N-protected isatin derivatives in one pot. Chiral 3,3'-disubstituted benzofuran-2(3H)-one derivatives bearing vicinal quaternary stereogenic centers, have been achieved with excellent yields (up to 98%), excellent enantioselectivities (up to 99:1 e.r.), and excellent diastereoselctivities (up to >20:1 dr).
URI: https://hdl.handle.net/10356/142580
Rights: This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Theses

Files in This Item:
File Description SizeFormat 
Thesis_Majhi Pankaj Kumar .pdf5.88 MBAdobe PDFView/Open

Page view(s)

32
checked on Sep 28, 2020

Download(s)

30
checked on Sep 28, 2020

Google ScholarTM

Check

Items in DR-NTU are protected by copyright, with all rights reserved, unless otherwise indicated.