Endocyclic restriction tests

A Refined Transition State Model for the SN2 Reaction Crossover Experiment and Endocyclic Restriction Test... 

P. Beak, Determinations of Transition-State Geometries by the Endocyclic Restriction Test Mechanism of Substitution at Nonstereogenic Atoms, Acc. Chem. Res. 1992, 25, 215-222 P. Beak, Mechanisms of Reactions at Nonstereogenic Heteroatoms Evaluation of Reaction Geometries by the Endocyclic Restriction Test, PureAppl. Chem. 1993, 65, 611-615. 

P. Beak, Mechanisms of reactions at nonstereogenic heteroatoms evaluation of reaction geometries by the endocyclic restriction test, Pure Appl. Chem. 1993, 65, 611-615. 

The transition state for oxygen transfer from iV-sulfonyloxaziridines to alkenes was studied by Anderson eta/, using the endocyclic restriction test <19990L1415>. In this study, molecules containing both the oxaziridine and alkene functionalities were prepared, and the ability of each system to intramolecularly transfer oxygen was evaluated. The results are consistent with a transition state in which N-0 bond cleavage is more advanced than C-O bond cleavage. 

Woods, K. W., Beak, P. The endocyclic restriction test an experimental evaluation of the geometry at oxygen in the transition structure for epoxidation of an alkene by a peroxy acid. J. Am. Chem. Soc. 1991, 113, 6281-6283. 

Another use of stereochemistry is a technique known as the endocyclic restriction test. In this procedure a cychc molecule is constructed so that two substituents might react with each other in a mechanism analogous to a bimolecular reaction. However, because the transition structure for the reaction must be cyclic, only one of two possible mechanisms is sterically feasible. Determining whether the intramolecular reaction can occur for transition structures with various ring sizes provides some insight into the probable geometry of the reactants in the bimolecular reaction. For an example, see Li, J. Beak, P. /. Am. Chem. Soc. 1992,114,9206. See also Beak, P. Acc. Chem. Res. 1992, 25, 215 Pure Appl. Chem. 1993, 65, 611. 

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