1560-02-7Relevant academic research and scientific papers
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.
Stereochemistry of the thermal isomerizations of (1/R,2R)-1-((E)-Styryl)-2-methylcyclopropane to 3-phenyl-4-methylcyclopentenes
Baldwin, John E.,Bonacorsi Jr., Samuel
, p. 10621 - 10627 (2007/10/02)
(1A,2R)-1-((E)-Styryl)-2-methylcyclopropane at 250 °C racemizes and isomerizes to 6-phenylhexa-1,4-(Z)-diene and to the four isomers of 3-phenyl-4-methylcyclopentene. From the measured rate constants for racemization and for structural isomerizations, and
The importance of conformation in the reactivity of radical cations. Changing configuration at saturated carbon centres
Perrott, Allyson L.,Arnold, Donald R.
, p. 272 - 279 (2007/10/02)
Irradiation of an acetonitrile solution of cis-1-methyl-2-phenylcyclopentane (1b cis); 1,4-dicyanobenzene (2), an electron-accepting photosensitizer; and 2,4,6-collidine (3), a nonnucleophilic base, leads to configurational isomerization of the cyclopenta
