Pr 1 1998 American Chemical Society, J. Am. Chem. Soc., Blackmond ja982448u Supporting Info Page 1 Supplementary Information (2 pages) Kinetic Implications of Nonlinear Effects in Asymmetric Synthesis“ Donna G. Blackmond Equations describing reaction rates and species concentrations as a function of reaction progress for reactions which are first-order in concentration of the chiral reagent but otherwise obey the assumptions of the ML; model for reactions using such a mixture of reagents: tty ta @ dd 7 14 = kaa @) fi) ty on k{ ° di tag Bt kala] [ad] = [dal], exr{—-k4st) a [a] = [4], exe{-kust) © [al] = [al], exp(-g* kat) o The cumulative batch enantioselectivity is calculated by summing the total concentrations of R and S products formed from the beginning of the reaction to time t. cumulative 66g = RES pot SR+ES ® R-product is formed in the reaction of dd with an enantioselectivity of ee,, in the reaction of // with an enantioselectivity of ee, and in the reaction of dl with an enantioselectivity of 0. S- product is formed in the reaction of dd with an enantioselectivity of -ce, in the reaction of i! with an enantioselectivity of ce, and in the reaction of dl with an enantioselectivity of 0. The definition of enantioselectivity allows us to describe the individual concentrations of R and S products produced from the reactions of each of the three chiral reagents present in the reaction mixture at any time t:© 1998 American Chemical Society, J. Am. Chem. Soc., Blackmond ja982448u Supporting Info Page 2 a R ee= ~ R+S P= total product = ass-(2)po( Sn a 2 ‘Assuming that the reaction stoichiometry is 1:1 between the chiral reagent and the product formed, we may calculate the total product P for each of the reactions using dd, Il, and dl. For example, the total amount of R and S product formed at time t from the reaction of dd is: Py, =(dd]] -[dd] = [da] -[da], exp(—kust) =[dd],(1—exp(-kw!)) 0) chiral reagent R-produet formed ‘S-product formed at time t at time t (! +68 Jaa, (1-exe(-kact) (: = Jel ~ex(-kut)) ( 1 Ye (ett) [Be jal —exy{-kuyt)) Slat] ((-exe(-2 eat) S[all ewe kut)) u“ a Inserting the sums of the R-products and the S-products into Eq. 8 gives the cumulative product enantioselectivty at time t for the first order reaction of the three chiral reagents.