1560-02-7Relevant articles and documents
Enantiodivergent Pd-catalyzed C–C bond formation enabled through ligand parameterization
Zhao, Shibin,Gensch, Tobias,Murray, Benjamin,Niemeyer, Zachary L.,Sigman, Matthew S.,Biscoe, Mark R.
, p. 670 - 674 (2018/11/01)
Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.
Photocleavage of Benzyl-Sulfide Bonds
Fleming, Steven A.,Jensen, Anton W.
, p. 7135 - 7137 (2007/10/02)
The nucleoside transport inhibitor 6--9-(β-D-ribofuranosyl)purine, NBMPR, has been used successfully in photoaffinity labeling.We have studied the mechanism for photocleavage of the benzyl-sulfur bond by using substituted benzyl phenyl sulfides as analogues of NBMPR.This has enabled us to enhance the photoreactivity of the benzyl-sulfur bond.We have also performed "radical clock" studies with a hexenyl side chain to trap reactive intermediates.The mechanistic interpretation from the substituent and side chain studies is that the benzyl-sulfur moiety is photocleaved via a homolytic pathway.
Organoyttrium-catalyzed cyclization of substituted 1,5- and 1,6-dienes
Molander, Gary A.,Hoberg, John O.
, p. 3123 - 3125 (2007/10/02)
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