Preecha Ngoviwatchai

Stereospecific vinyl substitutions occurring by free radical addition-elimination

Abstract The free radical chain reaction between cyclohexyl-HgCl and ( E ) or ( Z ) MeO 2 CCH=CHSnBu 3 , MeO 2 CCH=CHI, or ClCH=CHHgCl forms MeO 2 CCH=CHC 6 H 11 or ClCH=CHC 6 H 11 in a stereospecific manner with retention of stereochemistry.

Free radical substitution reactions of phenylacetylene derivatives by an addition-elimination mechanism

Phenylacetylenes (PhCCQ with Q = PhSO2, I, SPh, Bu3Sn PhCCHg) undergo free radical chain substitution reactions with RHgCl, R2Hg, (EtO)2P(O)HgCl, (PhS)2Hg or (PhSO2)2Hg. The relative reactivities of PhCCQ towards c-C6H11 · are Q = PhSO2 (65) > I (19) > Bu3Sn (1.0).

A comparison of the reactions of tert-butyl mercury and magnesium chlorides with β-styrenyl derivatives

Abstract Photostimulated substitution reactions of t-BuHgCl with PhCH=CHQ (Q = I, PhSO 2 , ClHg) proceed by a radical chain. With t -BuMgCl in THF, stereoselectivity excludes this process for Q = I but with Q = PhSO 2 (dark or hν) or HgCl (hν), radical substitution occurs.

Free Radical Processes in the Reactions of Organometallics with Organic Sulfur Compounds

Sulfur-centered radicals, RSO n • with n = 0 or 2 and presumably 1, react readily with certain organometallic reagents to generate alkyl radicals. These reactions can involve a formal SH2 substitution at a metal atom such as Li or Hg,1–3 e.g., reaction 1, or electron transfer with an easily oxidized organometallic species, reaction 2.3 The rates of reactions 1 and 2

Alkylation of .beta.-substituted styrenes by a free radical addition-elimination sequence

RSO_{n}^{\bullet }+{{R}^{1}}HgCl\to RS{{O}_{n}}HgX+{{R}^{1\bullet }}

Reaction of 1-alkenyl and 1-alkynyl derivatives of tin and mercury with hetero-centered radicals

(1)

Free radical chain reactions of ate complexes. Electron transfer processes 42

RSO_{n}^{\bullet }+{{\left( {{R}^{1}} \right)}_{2}}C{{u}^{-}}\to RSO_{n}^{-}+{{R}^{1\bullet }}+{{R}^{1}}Cu