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Controlled Acid‐Mediated Regioselective O ‐Desilylations for Multifunctionalization of Cyclodextrins
Author(s) -
Gu Jiamin,
Chen Tong,
Zhang Ping,
Ling ChangChun
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201402802
Subject(s) - chemistry , regioselectivity , silylation , silyl ether , tetra , reactivity (psychology) , cyclodextrin , surface modification , ether , combinatorial chemistry , organic chemistry , medicinal chemistry , stereochemistry , catalysis , medicine , alternative medicine , pathology
A highly valuable tri‐/tetra‐functionalization method is reported for cyclodextrin (CD) chemistry by taking advantage of the acid‐sensitivity of the O ‐silyl ether group and also the geometry of CD macrocycles. The controlled acid‐mediated O ‐desilylations from the easily accessible per‐3,6‐ O ‐silylated CD derivatives provide unprecedented regioselectivity to differentiate not only primary O ‐silyl groups from secondary groups, but also O ‐silyl groups of the same type with identical chemical reactivity. This methodology differs from other conventional monofunctionalization methods of natural CDs, which only allow for a direct twofold differentiation of hydroxyl groups in a CD, because the current method permits the synthesis of tri‐ and tetra‐functionalized CDs in a short reaction sequence. Most importantly, the developed method has been found to be applicable to all α‐, β‐, and γ‐CDs and the obtained CD intermediates are versatile. Furthermore, we demonstrate that these processes are practical and can be carried out on multigram scales.