Reactions of nucleophilic reagents with acylating agents of extreme reactivity and unreactivity. Correlation of .beta. values for attacking and leaving group variation

1970 ◽  
Vol 92 (18) ◽  
pp. 5442-5452 ◽  
Author(s):  
Alan R. Fersht ◽  
William P. Jencks
Keyword(s):  
Leaving Group ◽  
Group Variation ◽  
Nucleophilic Reagents

With Nucleophilic Reagents Having an α-Leaving Group

2002 ◽  
pp. 1
Author(s):  
S. Kobayashi ◽  
K. Manabe ◽  
H. Ishitani ◽  
J.-I. Matsuo
Keyword(s):  
Leaving Group ◽  
Nucleophilic Reagents

Leaving-group variation in aprotic Bamford-Stevens carbene generation

1978 ◽  
Vol 43 (1) ◽  
pp. 154-155 ◽  
Author(s):  
A. Richard Chamberlin ◽  
F. Thomas Bond
Keyword(s):  
Leaving Group ◽  
Group Variation

The Impact of Leaving Group Variation on the Anticancer Activity of Molybdenocenes

2018 ◽  
Vol 37 (21) ◽  
pp. 3909-3916 ◽  
Author(s):  
Wolfgang Kandioller ◽  
Marlene Reikersdorfer ◽  
Sarah Theiner ◽  
Alexander Roller ◽  
Michaela Hejl ◽  
...  
Keyword(s):  
Anticancer Activity ◽  
Leaving Group ◽  
Group Variation ◽  
The Impact

General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Chemical Space ◽  
Synthetic Approach ◽  
Asymmetric Cyclopropanation ◽  
Redox Active ◽  
Wide Range ◽  
Leaving Group ◽  
Stereoelectronic Properties ◽  
Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

Sign in / Sign up

Export Citation Format

Share Document