Highly stereoselective decarboxylation of (+)-1-Bromo-1-chloro-2,2,2-trifluoropropanoic acid gives (+)-1-Bromo-1-chloro-2,2,2-trifluoroethane ((+)-Halothane) with retention of configuration

The absolute configuration of the title acid (2) has been determined to be S by X-ray crystallography. Thus, decarboxylation of 2 produces (S)-(+)-halothane with 99% retention of configuration. This behavior is compared to other stereoselective decarboxylation reactions of ?-haloacids from the literature that also give high degrees of retention of configuration when in the form of their quaternary ammonium salts, which contain one proton. The proton of the ammonium salt is necessary to protonate the anionic intermediate formed from decarboxylation. In the absence of this relatively acidic proton, we had previously found that using triethylene glycol (TEG) as both solvent and proton source for the decarboxylation reaction of acid 2 caused poor stereoselectivity. This was in contrast to 1,2,2,2-tetrafluoro-1-methoxypropionic acid (6), which showed a high degree of retention of configuration in TEG. To rationalize this differing behavior we report DFT studies at PCM-B3LYP/6-31++G** level of theory (the results were additionally confirmed with 6-311++G** and aug-cc-pVDZ basis sets). The energy barrier to inversion of configuration of the anionic reaction intermediate of acid 2 (11) is 10.23 kcal/mol. However, we find that the anionic intermediate from acid 6 (10) would rather undergo ?-elimination instead of inversion of configuration. Thus the planar transition state required for inversion of configuration is never reached, regardless of the rate of proton transfer to the anion.

Tropical Atlantic SST during the mid-Pleistocene transition (MPT) of ODP Hole 175-1077B

We compare a new mid-Pleistocene sea surface temperature (SST) record from the eastern tropical Atlantic to changes in continental ice volume, orbital insolation, Atlantic deepwater ventilation, and Southern Ocean front positions to resolve forcing mechanisms of tropical Atlantic SST during the mid-Pleistocene transition (MPT). At the onset of the MPT, a strong tropical cooling occurred. The change from a obliquity- to a eccentricity-dominated cyclicity in the tropical SST took place at about 650 kyr BP. In orbital cycles, tropical SST changes significantly preceded continental ice-volume changes but were in phase with movements of Southern Ocean fronts. After the onset of large-amplitude 100-kyr variations, additional late glacial warming in the eastern tropical Atlantic was caused by enhanced return flow of warm waters from the western Atlantic driven by strong trade winds. Pronounced 80-kyr variations in tropical SST occurred during the MPT, in phase with and likely directly forced by transitional continental ice-volume variations. During the MPT, a prominent anomalous long-term tropical warming occurred, likely generated by extremely northward displaced Southern Ocean fronts. While the overall pattern of global climate variability during the MPT was determined by changes in mean state and frequency of continental ice volume variations, tropical Atlantic SST variations were primarily driven by early changes in Subantarctic sea-ice extent and coupled Southern Ocean frontal positions.