Theoretical studies of transition structures and stereoselectivities of the [2,3]-Wittig rearrangement of sulfur ylides

1991 ◽  
Vol 56 (19) ◽  
pp. 5657-5661 ◽  
Author(s):  
Yun Dong Wu ◽  
K. N. Houk
Keyword(s):  
Theoretical Studies ◽  
Sulfur Ylides ◽  
Wittig Rearrangement ◽  
Transition Structures

scholarly journals Experimental and theoretical studies of (4 + 1) annulations between α‐oxoketenes and stable phosphorous, nitrogen, or sulfur ylides

2019 ◽  
Vol 32 (6) ◽  
pp. e3939
Author(s):  
David Pierrot ◽  
Michel Rajzmann ◽  
Yannick Carissan ◽  
Jean Rodriguez ◽  
Damien Bonne ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Sulfur Ylides ◽  
Experimental And Theoretical Studies

scholarly journals Teaching an old carbocation new tricks: Intermolecular C–H insertion reactions of vinyl cations

Science ◽  
2018 ◽  
Vol 361 (6400) ◽  
pp. 381-387 ◽  
Author(s):  
Stasik Popov ◽  
Brian Shao ◽  
Alex L. Bagdasarian ◽  
Tyler R. Benton ◽  
Luyi Zou ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Computational Studies ◽  
Mechanistic Studies ◽  
Insertion Reactions ◽  
Bond Forming ◽  
The Past ◽  
Carbon Carbon Bond ◽  
Transition Structures ◽  
The Subject ◽  
Experimental And Theoretical Studies

Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.

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