The Study On 1,2-Diamination Of Arenes With Domino Aryne Precursors

Arylamine is an important structure in organic compounds; this structural motif often exists in natural products, biologically active molecules, drugs, dyes and organic molecular materials. Via simple and fast method to assemble such structures is an important research area in synthetic organic chemistry. Among them, those with two amine groups on the aromatic ring are also important structures. The synthesis of these structures, however, usually requires multi-step manipulations and purifications, which restricts the broad application of these methods. Using transition-metal catalyzed coupling reactions can synthesize these diaminoarenes, but the synthesis of unsymmetrical products still requires multi-step process. Moreover, the late-stage of the synthetic route requires transitional metal-free conditions in industry drug production. Therefore, searching for simple and quick way to achieve the synthesis of such diaminoarenes still attracts the attention of many synthetic organic chemists.In this project, we used domino aryne precursors(TPBT) to react with diamine substrates(sulfonyl group-bridged diamines). After a series of condition optimization, we efficiently prepared ortho-diaminobenzenes. On the basis of this work, we are continuing to expand the substrate scope, and found that the reaction is not only applicable to symmetrical aromatic amines as well as alkyl amines, but also applicable to unsymmetric diamine substrates.In addition, we tried our effort in attempting to use sodium phenylsulfamate as the substrate to react with TPBT in order to obtain N, O-functionalized arenes, and got moderate yield. Besides, we also planned to introduce migrating groups(such as allyl, Boc, etc.) in the substrate, which are expecting to react with TPBT in a manner to incorporate the 1, 2, 3-positions of the arene ring. So far, this study has yet got the desired results.