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. Author manuscript; available in PMC: 2019 Oct 31.
Published in final edited form as: J Am Chem Soc. 2019 Jul 19;141(30):11892–11904. doi: 10.1021/jacs.9b02893

Figure 7.

Figure 7.

Contributions of different types of nucleophile-substrate interactions to the regioselectivity in neutral Pd(OAc)2-catalyzed cis- and trans-aminopalladation with phthalimide anion. The computed regioselectivity (DDE‡) is calculated from the energy difference between Markovnikov and anti-Markovnikov transition states (DDE‡ = DEM‡ – DEA‡). Each energy component (DDEsteric, DDEelstat, DDEorbital, and DDEdisp) is calculated in a similar fashion (DDE = DEM – DEA). Positive DDE values indicate effects that promote anti-Markovnikov addition; negative DDE values indicate effects that promote Markovnikov addition. All energies are in kcal/mol. The π→d charge transfer energies (DEct) in 9M-TS and 9A-TS were calculated using COVP analysis (the donor orbital is shown in solid; the acceptor orbital is shown in transparent). The molecular orbital coefficients of the C=C double bond in alkene 1 was calculated at B3LYP/6–31G(d) level.