Please use this identifier to cite or link to this item: https://scholarbank.nus.edu.sg/handle/10635/138148
Title: PART I: APPLICATIONS OF SEMIPINACOL REARRANGEMENT REACTIONS ON THE SYNTHESIS OF MACROCYCLIC KETONES AND AXIALLY CHIRAL BIARYLS; PART II: SYNTHESIS AND CHARACTERIZATION OF BENZO [1,2-C,4,5-C']BIS[1,2,5]THIADIAZOLE BASED DIRADICALOIDS AND NEAR-INFRARED DYES
Authors: LIU YI
Keywords: Semipinacol rearrangement, macrocyclic ketones, axially chiral biaryls, benzo[1,2-c,4,5-c']bis[1,2,5]thiadiazole, diradicaloids, NIR dyes
Issue Date: 10-Aug-2017
Citation: LIU YI (2017-08-10). PART I: APPLICATIONS OF SEMIPINACOL REARRANGEMENT REACTIONS ON THE SYNTHESIS OF MACROCYCLIC KETONES AND AXIALLY CHIRAL BIARYLS; PART II: SYNTHESIS AND CHARACTERIZATION OF BENZO [1,2-C,4,5-C']BIS[1,2,5]THIADIAZOLE BASED DIRADICALOIDS AND NEAR-INFRARED DYES. ScholarBank@NUS Repository.
Abstract: In part I, the synthesis of macrocyclic ketones remains challenging, due to the ring strain and/or entropic loss in their formation step. Electrophilic halogen-initiated semipinacol rearrangement is rarely used to approach macrocylic ketones. A series of macrocylic ketones including the natural product, rac-muscone, have been prepared using semipinacol rearrangement. The rearranged products could further undergo Dowd-Beckwith rearrangement reactions to afford cyclic -substituted ketones. We elaborated the asymmetric semipinacol rearrangement reactions to synthesize axially chiral biaryls in a dynamic-kinetic resolution/point-to-axial chirality transfer strategy. Under the established conditions, axially chiral biaryls were obtained in good atroposelectivity and diastereoselectivity. In part II, we synthesized two series of BBT-based compounds. X-ray crystallographic analysis confirmed the partial aromaticity recovery of the thiadiazole ring. Magnetic measurements revealed that some of them exhibit considerable diradical character and a small singlet-triplet energy gap. The NIR absorption of these BBT oligomers implies their potential application.
URI: http://scholarbank.nus.edu.sg/handle/10635/138148
Appears in Collections:Ph.D Theses (Open)

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