79894-59-0Relevant articles and documents
Highly regioselective hydrosilylation of unsymmetric alkynes using a phenylthio directing group
Huang, Kuan-Hsun,Isobe, Minoru
, p. 4733 - 4740 (2014/08/05)
Cobalt-assisted hydrosilylation of acetylenes is particularly interesting in organic synthesis since alkynyl group functionalization can give way to more useful substructures. This study aims to answer the general question of how to control hydrosilylatio
Reactivity of individual organolithium aggregates: A RINMR study of n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium
Jones, Amanda C.,Sanders, Aaron W.,Bevan, Martin J.,Reich, Hans J.
, p. 3492 - 3493 (2008/01/01)
Low-temperature rapid injection NMR (RINMR) experiments were performed on two lithium reagents, n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium (5), with the goal of measuring the relative reactivity of the different aggregates (dimer, mixed dimer, and tetramer for n-BuLi, monomer and tetramer for 5) toward typical electrophiles. The reaction of the n-BuLi dimer with (trimethylsilyl)acetylene first forms the mixed dimer n-BuLi·Me3SiC≡CLi, which is about 1/60 as reactive as the n-BuLi homodimer. The tetramer does not react. In the deprotonation of (phenylthio)acetylene, the n-BuLi dimer was found to be 3.5 × 108 as reactive as the tetramer, and in the addition to p-diethylaminobenzaldehyde, the relative reactivity was at least 2 × 104. In the deprotonation of (p-tolylsulfonyl)acetylene, the monomer of 5 was at least 1014 times as reactive as the tetramer. These measurements show that the difference in reactivity between the lower and higher aggregates of organolithium reagents can be many orders of magnitude higher than all previous estimates. Copyright
