Development of Small-Molecules-Activation Reactions By Utilizing Abundant Main Group Elements

2021 Fiscal Year Final Research Report

• Project/Area Number: 19H02705
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: University of Tsukuba (2020-2021); Nagoya City University (2019)
• Principal Investigator: Sasamori Takahiro 筑波大学, 数理物質系, 教授 (70362390)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Keywords: 典型元素 / 小分子活性化 / ケイ素 / リン / 立体保護 / 低配位化学種

Outline of Final Research Achievements

The catalytic activation of neutral small molecules followed by the formation of C-C bonds is a highly important method to increase the complexity and value of simple starting materials. Traditionally, transition-metal catalysts have been used for this purpose. However, similar C-C coupling reactions of neutral small organic molecules in the absence of a transition-metal catalyst remain largely unknown, although such “transition-metal-free” catalytic systems would be highly desirable in order to avoid the use of precious metals.
We have found that a bromogermylene, which is a divalent species of main group element "Ge", underwent alkyne activation as well as the reactions of transition metals. In addition, we have succeeded in the synthesis of "bottleable" synthones of a divalent species of "Si" and dicoordinated "P" cation, which are known to be very reactive towards small molecules.

Free Research Field

典型元素化学、有機化学、有機金属化学

Academic Significance and Societal Importance of the Research Achievements

稀少な遷移金属を使わなくてはならないと認識されている、有機反応化学において重要な、小分子活性化反応について、豊富に存在する、ケイ素などの典型元素であっても、適切な分子設計を施せば、アルキンやオレフィンなどの中性小分子を活性化することができることを見出した。稀少な元素を豊富な元素で置き換える「元素戦略」の観点からみても、遷移金属が必須と考えられている有機反応を典型元素で代替できる可能性があることを示した本研究課題は、豊富な典型元素の触媒開発にむけて、基盤となる重要な知見と、研究分野に対する大きな波及効果を与えた。