An efficient synthesis of arylazulenes involving minimal steps was developed. The combination of Pd(OAc) 2 / XPhos as ac atalysta nd pivalica cid as an additive was key for the direct arylation of CÀHb onds, and the reactionp roceeded preferentially at the 1-and 3-positions of azulene, without heteroatom-containing directing groups. Compared with the traditional cross-coupling protocol, the arylation method described here requires fewer steps and uses commerciallya vailables ynthetic blocks. The degree of conjugation and the optical properties of the resulting azulenec onjugates can be adjusted by simple protonation, whicha llows the current method to be an efficient strategy for exploiting novel azulene-based functional materials.[a] Dr.

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