355121-52-7Relevant articles and documents
Large scale synthesis of the Cdc42 inhibitor secramine A and its inhibition of cell spreading
Xu, Bo,Pelish, Henry,Kirchhausen, Tomas,Hammond, Gerald B.
, p. 4149 - 4157 (2008/09/19)
We describe a large scale synthesis of secramine A. Consistent with its ability to inhibit activation of the small GTPase Cdc42, we find that secramine A inhibits cell spreading, a process previously shown to be Cdc42-dependent. The Royal Society of Chemistry 2006.
Experimental and theoretical studies on the thermal decomposition of heterocyclic nitrosimines
Bartsch,Yeh Moon Chae,Ham,Birney
, p. 7479 - 7486 (2007/10/03)
A series of substituted 2-nitrosiminobenzothiazolines (2) were synthesized by the nitrosation of the corresponding 2-iminobenzothiazolines (6). Thermal decomposition of 2a-f and of the seleno analogue 7 in methanol and of 3-methyl-2-nitrosobenzothiazoline (2a) in acetonitrile, 1,4-dioxane, and cyclohexane followed first-order kinetics. The activation parameters for thermal deazetization of 2a were measured in cyclohexane (ΔH? = 25.3 ± 0.5 kcal/mol, ΔS? = 1.3 ± 1.5 eu) and in methanol (ΔH? = 22.5 ± 0.7 kcal/mol, ΔS? = -12.9 ± 2.1 eu). These results indicate a unimolecular decomposition and are consistent with a proposed stepwise mechanism involving cyclization of the nitrosimine followed by loss of N2. The ground-state conformations of the parent nitrosiminothiazoline (9a) and transition states for rotation around the exocyclic C=N bond, electrocyclic ring closure, and loss of N2 were calculated using ab initio molecular orbital theory at the MP2/6-31G* level. The calculated gas-phase barrier height for the loss of N2 from 9a (25.2 kcal/mol, MP4(SDQ, FC)/6-31G*//MP2/6-31G* + ZPE) compares favorably with the experimental barrier for 2a of 25.3 kcal/mol in cyclohexane. The potential energy surface is unusual; the rotational transition state 9a-rot-ts connects directly to the orthogonal transition state for ring-closure 9aTS. The decoupling of rotational and pseudopericyclic bond-forming transition states is contrasted with the single pericyclic transition state (15TS) for the electrocyclic ring-opening of oxetene (15) to acrolein (16). For comparison, the calculated homolytic strength of the N-NO bond is 40.0 kcal/mol (MP4(SDQ, FC)/6-31G* + ZPE).