JACS: the first case of Suzuki reaction catalyzed by non transition metals

The coupling reaction of organic boron reagent and organic electrophilic reagent, namely Suzuki miyaara coupling reaction, is the most effective method for people to construct carbon carbon bond at present The award of 2010 Nobel Prize confirmed its contribution to human society In the past 50 years, transition metals as catalysts have played a key role in the development of such reactions However, due to the limitations of their own reaction characteristics, transition metals are also facing many challenges For example, the reaction activity of SP 2 hybrid aryl halides is higher than that of SP 3 hybrid alkyl halides When there are many kinds of carbon halogen bonds in the molecule, it is a big problem to selectively preferentially convert the alkyl carbon halogen bonds Huang Yong research group of Shenzhen Graduate School of Peking University, in order to solve this problem, a new way is proposed to find a coupling process different from transition metal catalysis and realize the target of Suzuki coupling reaction under non transition metal catalysis or no transition metal catalysis mechanism They believe that the introduction of the new catalytic mechanism can provide the complementary reaction activity with the traditional transition metal catalytic process, and will greatly supplement the current synthesis methodology In response to this goal, Huang Yong group developed a new type of organic thioether catalyst, and realized the first Suzuki coupling reaction with non transition metal but organic small molecule as catalyst The result was recently published on J am Chem SOC., entitled a transition metal free Suzuki type cross coupling reaction of benzyl halides and bosonic acids via 1,2-metallic shift 。
The Suzuki coupling reaction catalyzed by organic small molecules (source: J am Chem SOC.) Huang Yong's group received organoboron compound 1, Inspired by 2-transfer reaction (1979 Nobel Prize reaction) and thiohilide chemistry, using the resolving power of nucleophilic substitution reaction in basic organic chemistry for alkyl and aryl electrophilic reagents, an intermediate (zwitteriodicate complex) containing both positive and negative charges was conceived Based on this, the catalytic mechanism of organic small molecules was deduced Benzyl halogenated hydrocarbon and aryl phenylboric acid were studied as model reactions to optimize the catalyst structure Finally, not only the first non transition metal catalyzed Suzuki reaction was realized, but also the reaction activity complementary to the traditional transition metal catalytic mechanism was obtained In the new catalytic system, the selectivity of alkyl electrophilic reagent is much higher than that of aryl electrophilic reagent In the traditional coupling reaction, the most active aryl carbon iodine bond and aryl carbon bromine bond are not affected in the new catalytic system, and can be retained in the product, and provide a reaction site for the subsequent flow-through derivative synthesis The preliminary mechanism experiment also verified the designed catalytic mechanism and provided a new idea for the development of cross coupling reaction in the future Representative substrates and Applications (source: J am Chem SOC.) Under the guidance of Professor Huang Yong of Shenzhen Graduate School of Peking University, the above work was completed by postdoctoral students, Zhiqi and song Feifei, Ph.D., in cooperation with Dr Sun Huan Relying on the chemical genomics platform of Shenzhen Graduate School of Peking University, the above work was obtained from the National Natural Science Foundation of China, Guangdong special branch program, Guangdong Natural Science Foundation, Shenzhen peacock team program and Shenzhen Science and technology innovation program Funding from the new committee Article link: http://pubs.acs.org/doi/10.1021/jacs.8b00380 corresponding author: Huang Yong http:// M = Content & C = index & A = lists & catid = 157