119th General Meeting of the KCS

Type Symposium
Area [SRC 심포지엄] New Trends and Developments in Organic Synthesis
Room No. 303호
Time WED 17:00-:
Code KCS5-14
Subject Development of Novel Synthetic Routes for Axially Chiral BISESAMOL Derivatives
Authors 조영인, 천철홍*
고려대학교 화학과, Korea
Abstract Axially chiral biaryl diol derivatives, such as BINOL and VAPOL, have been widely used as either chiral ligands in metal-catalyzed asymmetric catalysis or chiral building blocks in chiral Brønsted acid catalysis. Since both substituents and dihedral angles along the chiral axis turn out to play a significant role in the reactivity and selectivity in asymmetric transformation with the biaryl diols, numerous efforts have been made to develop various axially chiral biaryl diol derivatives. However, the effect of dihedral angle has been rather poorly investigated compared to that of substituents; although there are a number of methods for the preparation of axially chiral binaphthol derivatives, such as BINOL or octahydroBINOL, no general synthetic routes for other axially chiral biaryl diols have been developed yet. To address this problem, our group have developed the synthetic pathways of chiral 3,3’-disubstituted 1,1’-bi-2-phenol (BIPhOL) derivatives via diastereomeric resolution using a boronic acid moiety as a resolving group followed by Suzuki-Miyaura reaction.1 In addition, we attempted to develop divergent synthetic routes for other BIPhOL derivatives, such as 1,1’-BISESAMOL, from the same chiral boronic acid intermediate through oxidation of the boronic acid followed by methylenation. However, the desired product was not obtained and unexpected side-product was generated. Alternatively, we developed a route for BISESAMOL through the diastereomeric resolution of BISESAMOL boronic acid using a boronic acid moiety as a resolving group. Subsequent derivatization of the boronic acid moieties at the 3,3’-positions allowed us to prepare several BISESAMOL derivatives. In this presentation, we will present the recent progress in the synthesis of axially chiral BIPhOL derivatives. Reference 1. Yoon, J.-M.; Lee, C.-Y.; Jo, Y.-I.; Cheon, C.-H. J. Org. Chem. 2016, 81, 8464.
E-mail jyisky5@naver.com