ChemInform Abstract: Use of Hydroxide Ion as Leaving Group in Photosolvolysis Reactions

ChemInform ◽  
2010 ◽  
Vol 25 (26) ◽  
pp. no-no
Author(s):  
D. SHUKLA ◽  
P. WAN
Keyword(s):  
2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  

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>


1997 ◽  
Vol 12 (4) ◽  
pp. 225-229
Author(s):  
Cart-in A-S. Gustavsson ◽  
Chritofer T. Lindgren ◽  
Mikael E. Lindström

Abstract The amount of lignin reacting according to the slow residual phase, i.e. the residual phase lignin, is in many perspectives an interesting issue. The purpose of the present investigation was to develop a mathematical model to show how the amount of residual phase lignin in the kraft cooking of spruce chips (Picm ahies) depends on the conditions in the earlier phases of the cook. The variables studied were hydroxide ion concentration, hydrogen sulfide ion concentration and ionic strength. The liquor-to-wood ratio during pulping was very high to maintain approximately constant chemical concentrations throughout each experiment (so called "constant composition" cooks). An increase in hydroxide ion concentration andtor hydrogen sulfide ion concentration leads to a decrease in the amount of residual phase lignin, while an increase in ionic strength, i.e. sodium ion concentration, leads to an increase. A signiticant result is that the hydrogen sulfide ion concentration has a pronounced influence on the amount of residual phase lignin during a cook at a low hydroxide ion concentration. The amount of residual phase lignin expressed as % lignin on wood, L,, can be described by the following equation developed for "constant composition" cooks (when cooking with a constant sodium ion concentration of 2 mol/L): LT=0,55-0.32*[HO-](-1,3)*ln[HS-] This equation is valid for a concentration of HO- in the range from 0.17 to 1.4, and a hydrogen sulfide ion concentration from 0.07 to 0.6 mol/L.


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