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. Author manuscript; available in PMC: 2017 Jun 29.
Published in final edited form as: J Am Chem Soc. 2016 Jun 15;138(25):7832–7835. doi: 10.1021/jacs.6b03786

Figure 3.

Figure 3

The HDDA cycloisomerization (i.e., 16 to 17) proceeds via diradical 18 rather than through a “concerted TS” geometry; the relative rate data indicate that the “stepwise TS1” defines the rate of reaction.