%0 Generic
%A Denmark, Scott E.
%A Jaunet, Alex
%D 2014
%T Catalytic, Enantioselective,
Intramolecular Carbosulfenylation of Olefins. Preparative and Stereochemical
Aspects
%U https://acs.figshare.com/articles/dataset/Catalytic_Enantioselective_Intramolecular_Carbosulfenylation_of_Olefins_Preparative_and_Stereochemical_Aspects/2336191
%R 10.1021/jo4023765.s002
%2 https://acs.figshare.com/ndownloader/files/3973801
%K Intramolecular Carbosulfenylation
%K alkene structure
%K site selectivity
%K Br ønsted acid
%K cocatalytic Br ønsted acid
%K BINAM
%K Stereochemical AspectsThe
%X The
first catalytic, enantioselective, intramolecular carbosulfenylation
of isolated alkenes with aromatic nucleophiles is described. The combination
of N-phenylsulfenylphthalimide, a chiral
selenophosphoramide derived from BINAM, and ethanesulfonic
acid as a cocatalytic Brønsted acid induced an efficient and
selective cyclofunctionalization of various alkenes (aliphatic
and aromatic) tethered to a 3,4-methylenedioxyphenyl
ring. Under these conditions, 6-phenylthio-5,6,7,8-tetrahydronaphthalenes
are formed diastereospecifically in good yields (50–92%)
and high enantioselectivities (71:29–97:3 er). E-Alkenes reacted much more rapidly and with much higher
selectivity than Z-alkenes, whereas electron-rich
alkenes reacted more rapidly but with comparable selectivity to electron-neutral
alkenes and electron-deficient alkenes. The Brønsted acid played
a critical role in effecting reproducible enantioselectivity. A model
for the origin of enantioselectivity and the dependence of rate and
selectivity on alkene structure is proposed along with a rationale
for the site selectivity in reactions with monoactivated arene
nucleophiles.
%I ACS Publications