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Stereoselective Propargylations with Transition‐Metal‐Stabilized Propargyl Cations
Author(s) -
Müller Thomas J. J.
Publication year - 2001
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 - 10.1002/1099-0690(200106)2001:11<2021::aid-ejoc2021>3.0.co;2-g
Subject(s) - propargyl , chemistry , nucleophile , cationic polymerization , stereoselectivity , transition metal , nucleophilic addition , triple bond , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , catalysis , double bond
Cationic propargylations have been known for quite some time but only the advent of transition metal stabilization has initiated their stereoselective applications. The introduction of nucleophilic additions to dicobalthexacarbonyl‐complexed propargyl cations, known as the Nicholas reaction, has led to widespread applications in the synthesis of complex molecules. Besides the stabilization by direct complexation of the triple bond, the complementary mode, i.e. transition metal complex substituents as propargyl cation stabilizing functional groups, is almost unknown. However, upon ionization, ferrocenyl‐ and (arene)chromiumcarbonyl‐substituted propargyl derivatives give the desired cationic species, and these cations can be regarded as quite reactive propargyl cations without simultaneous complexation of the triple bond, thus enabling highly diastereoselective nucleophilic additions with the potential of exploiting the ambident nature of propargyl cations.