Carbon−Sulfur Bond-Forming Reductive Elimination Involving sp-, sp2-, and sp3-Hybridized Carbon. Mechanism, Steric Effects, and Electronic Effects on Sulfide Formation

1998 ◽  
Vol 120 (36) ◽  
pp. 9205-9219 ◽  
Author(s):  
Grace Mann ◽  
David Baranano ◽  
John F. Hartwig ◽  
Arnold L. Rheingold ◽  
Ilia A. Guzei
Keyword(s):  
Reductive Elimination ◽  
Steric Effects ◽  
Electronic Effects ◽  
Bond Forming ◽  
Sulfur Bond

scholarly journals Carbon(sp3)-nitrogen bond-forming reductive elimination from phosphine-ligated alkylpalladium(II) amide complexes: A DFT study

Tetrahedron ◽  
2019 ◽  
Vol 75 (2) ◽  
pp. 137-143 ◽  
Author(s):  
Quan Jiang ◽  
D. Matthew Peacock ◽  
John F. Hartwig ◽  
Thomas R. Cundari
Keyword(s):  
Reductive Elimination ◽  
Dft Study ◽  
Bond Forming ◽  
Nitrogen Bond

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes

1980 ◽  
Vol 58 (24) ◽  
pp. 2737-2744 ◽  
Author(s):  
Dennis G. Garrattz ◽  
Pierre L. Beaulieu
Keyword(s):  
Positive Charge ◽  
Steric Effects ◽  
Rate Data ◽  
Electronic Effects ◽  
Rate Determining Step ◽  
Minimal Importance ◽  
Electrophilic Additions

The role of steric and electronic effects during the rate and product determining steps for the addition of arenesulphenyl chlorides to 1,3-disubstituted allenes has been briefly examined. Both effects appear to be generally of minimal importance during the rate determining step. The available rate data indicate the presence of little, if any, build up of positive charge on sulphur. These results are interpreted in terms of an SN2 attack on bivalent sulphur leading to an alkylidenethiiranium ion intermediate. Steric effects are of greater importance in the product determining step, particularly when the sulphenyl chlorides possess two bulky ortho substituents, as in the case of 2,4,6-triisopropylbenzenesulphenyl chloride.

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