68979-89-5Relevant academic research and scientific papers
Carbonylative C-C bond activation of aminocyclopropanes using a temporary directing group strategy
Wang, Gang-Wei,Sokolova, Olga O.,Young, Tom. A.,Christodoulou, Ektor M. S.,Butts, Craig P.,Bower, John F.
supporting information, p. 19006 - 19011 (2020/11/13)
Temporary directing groups (TDGs) underpin a range of C-C bond activation methodologies; however, the use of TDGs for the regiocontrolled activation of cyclopropane C-C bonds is underdeveloped. In this report, we show how an unusual ring contraction process can be harnessed for TDG-based carbonylative C-C bond activations of cyclopropanes. The method involves the transient installation of an isocyanate-derived TDG, rather than relying on carbonyl condensation events as used in previous TDG-enabled C-C bond activations.
Modular Access to Substituted Azocanes via a Rhodium-Catalyzed Cycloaddition-Fragmentation Strategy
Shaw, Megan H.,Croft, Rosemary A.,Whittingham, William G.,Bower, John F.
supporting information, p. 8054 - 8057 (2015/07/15)
A short entry to substituted azocanes by a Rh-catalyzed cycloaddition-fragmentation process is described. Specifically, exposure of diverse N-cyclopropylacrylamides to phosphine-ligated cationic Rh(I) catalyst systems under a CO atmosphere enables the directed generation of rhodacyclopentanone intermediates. Subsequent insertion of the alkene component is followed by fragmentation to give the heterocyclic target. Stereochemical studies show, for the first time, that alkene insertion into rhodacyclopentanones can be reversible.
Reactions of Cyclopropyl Sulfonates with Nucleophiles: SN2 Displacements at Cyclopropanes with Inversion
Banert, Klaus
, p. 1564 - 1574 (2007/10/02)
Treatment of cyclopropyl trifluoromethanesulfonate (3) with tributylhexadecylphosphonium azide (QN3) in aprotic solvents almost quantitatively afforded cyclopropyl azide (6) in a second-order reaction.Nucleophilic displacements with ring preservation were also achieved using QCN or QBr.The analogous reactions of the epimeric 2-methylcyclopropyl trifluoromethanesulfonates (16, 17) with QN3 highly stereospecifically yielded the 2-methylcyclopropyl azides (24, 25) with inversion in addition to the allylic azides 27, 28, and 29.The product fraction of cyclic azides decrea sed with growing steric hindrance in the order 3 > 16 > 17.The experimental results show that SN2 displacements take place with clean inversion at the cyclopropane carbon atom.
