Taking into account the particularly mild reaction conditions and additive-free setup, Mn4 could be a promising choice for transformations in pharmaceutical settings. Encouraged by these findings we envisioned the application of Mn4 for the gram-scale synthesis of E-4-(prop-1-en-1-yl)-1,1'-biphenyl from 4-allyl-1,1'-biphenyl (Scheme 1, 8a). With biphenyl scaffolds composing many biologically active molecules and pharmaceuticals, 19 this building block seemed a worthwhile target for this demonstration. Preliminary studies on long distance isomerization (chain walking) were conducted by increasing the reaction temperature. At room temperature olefins 11 and 12 were converted into 11a and 12b, respectively in 68 and 95 % yields with E/Z ratios of 81:19 and 86:14 (Scheme 2). Upon addition of a new batch of catalyst, at 70 °C these olefins were further converted into the conjugated analogues 11b and 12b in 89 and 48 % yields, respectively, with E/Z ratios of 90:10 and 99:1. It should be noted that in the case of the non-branched terminal alkene 11 partial chain-walking occurred already at room temperature accounting for the lower yield of 11a. For the sterically more demanding 12a, the second transposition step is significantly more difficult even at a reaction temperature of 70 °C leading to a lower yield of 12b. The formation of 11b and 12b from 11 and 12, respectively, was also achieved in one step with similar yields and E/Z ratios upon performing the reaction at 70 o C for 18 h. It has to be mentioned that in the case of the aliphatic substrates 15 and 16 no chain walking was observed.