Excitation with shaped femtosecond laser pulses is a logical extension of coherent two-dimensional (2D) spectroscopy. Here we combine quantum control and information from 2D spectroscopy to analyze the initial steps in three competing reaction pathways of an isomerizing merocyanine dye. Besides the achievement of control objectives, we show how excitation with tailored pulses can be used to retrieve photochemical information that is inaccessible or experimentally demanding to obtain with other approaches.