Mercuration of calix[4]arenes immobilized in the 1,2- and 1,3-alternate conformations

TY - JOUR

T1 - Mercuration of calix[4]arenes immobilized in the 1,2- and 1,3-alternate conformations

AU - Slavík, Petr

AU - Eigner, Václav

AU - Böhm, Stanislav

AU - Lhoták, Pavel

PY - 2017/5/10

Y1 - 2017/5/10

N2 - Calix[4]arenes immobilized in the 1,2-alternate and 1,3-alternate conformations were directly mercurated using Hg(TFA)2. The reaction regioselectivity was compared with the thermodynamic stability of the corresponding products obtained by theoretical calculations (wB97XD/def2tzvp method). Both experimental and theoretical data suggest that para substitution is slightly preferred over meta attack for the 1,2-alternate conformer, while in the case of the 1,3-alternate conformation the situation is reversed. The usefulness of the mercury intermediates was demonstrated by the synthesis of a rigid upper-rim-bridged calixarene in the 1,2-alternate conformation possessing a highly distorted cavity. A simple transformation of the organomercury compounds afforded the corresponding iodo derivatives, which are potentially applicable as building blocks for further synthesis. Moreover, many products are inherently chiral representing unique substitution patterns inaccessible by common “mercury-free” chemistry.

AB - Calix[4]arenes immobilized in the 1,2-alternate and 1,3-alternate conformations were directly mercurated using Hg(TFA)2. The reaction regioselectivity was compared with the thermodynamic stability of the corresponding products obtained by theoretical calculations (wB97XD/def2tzvp method). Both experimental and theoretical data suggest that para substitution is slightly preferred over meta attack for the 1,2-alternate conformer, while in the case of the 1,3-alternate conformation the situation is reversed. The usefulness of the mercury intermediates was demonstrated by the synthesis of a rigid upper-rim-bridged calixarene in the 1,2-alternate conformation possessing a highly distorted cavity. A simple transformation of the organomercury compounds afforded the corresponding iodo derivatives, which are potentially applicable as building blocks for further synthesis. Moreover, many products are inherently chiral representing unique substitution patterns inaccessible by common “mercury-free” chemistry.

KW - Bridgíng

KW - Calix[4]arene

KW - Mercuration

KW - Regioselectivity

UR - http://www.scopus.com/inward/record.url?scp=85017199313&partnerID=8YFLogxK

U2 - 10.1016/j.tetlet.2017.03.085

DO - 10.1016/j.tetlet.2017.03.085

M3 - Article

AN - SCOPUS:85017199313

SN - 0040-4039

VL - 58

SP - 1846

EP - 1850

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 19

ER -