Lithium Diisopropylamide: Nonequilibrium Kinetics and Lessons Learned about Rate Limitation.

ABSTRACT: The kinetics of lithium diisopropylamide (LDA) in tetrahydrofuran under nonequilibrium conditions are reviewed. These conditions correspond to a class of substrates in which the rates of LDA aggregation and solvation events are comparable to the rates at which various fleeting intermediates react with substrate. Substrates displaying these reactivities, by coincidence, happen to be those that react at tractable rates on laboratory time scales at -78 °C. In this strange region of nonlimiting behavior, rate-limiting steps are often poorly defined, sometimes involve deaggregation, and at other times include reaction with substrate. Changes in conditions routinely cause shifts in the rate-limiting steps, and autocatalysis is prevalent and can be acute. The studies are described in three distin

SUBMITTER: Algera RF 

PROVIDER: S-EPMC6059656 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature