Asymmetric Borylation of Remote C(sp3)-H Bonds for the Construction of Compounds with Three-Dimensional Structural Diversity

远程 C(sp3)-H 键的不对称硼化用于构建具有三维结构多样性的化合物

• 批准号: 20K15269
• 负责人: REYES RONALD・LAZO
• 金额: $ 2.66万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Early-Career Scientists
• 财政年份: 2020
• 资助国家: 日本
• 起止时间: 2020-04-01 至 2023-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-20K15269/
• 关键词: borylation; asymmetric synthesis; organometallic catalysis; organic synthesis; C-H activation; C-H functionalization; remote C-H bonds; noncovalent interactions

With our interest in the development of novel methodologies for the transformation of C-H bonds in readily available feedstock chemicals, we previously demonstrated the competent activation and subsequent asymmetric borylation of g-C(sp3)-H bonds under Ir catalysis. Our collaboration with ICReDD scientists has given us infinite opportunity to further extend the reactivity of our catalytic system. Thus, guided by calculation derived transition-state models, we recently succeeded in the asymmetric borylation of more distal C-H bonds in the aliphatic hydrocarbon chain of common and readily available chemical feedstocks including biomass resources allowing for a more sustainable and efficient organic synthesis. Thereby, the borylation of e-C-H bonds, located five carbons away from the carbonyl group of the substrate, has been achieved - a direct functionalization realized using a modularly designed supramolecular catalytic assembly.

随着我们的兴趣在开发新的方法转化的C-H键在现成的原料化学品，我们以前证明了主管激活和随后的不对称硼基化的g-C（sp3）-H键Ir催化下。我们与ICReDD科学家的合作为我们提供了无限的机会来进一步扩展我们催化系统的反应性。因此，通过计算导出的过渡态模型的指导，我们最近成功地在常见的和容易获得的化学原料（包括生物质资源）的脂肪烃链中的更远侧C-H键的不对称硼基化，从而允许更可持续和有效的有机合成。因此，已经实现了位于距离基底的羰基5个碳的e-C-H键的硼基化-使用模块化设计的超分子催化组装体实现的直接官能化。

项目成果

Dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin, 4-[[(1R)-2'-[(triisopropylsilyl)oxy][1,1'-binaphthalen]-2-yl]oxy]-, (11bR)-(9CI).

二萘并[2,1-d:1,2-f][1,3,2]二氧磷杂磷，4-[[(1R)-2-[(三异丙基甲硅烷基)氧基][1,1-联萘]

• 发表时间: 2020
• 期刊: Encyclopedia of Reagents for Organic Synthesis
• 作者: Reyes;R. L. and Sawamura;M.
• 通讯作者: M.

Asymmetric Remote C-H Bond Borylation with a Modular Iridium Catalyst

使用模块化铱催化剂进行不对称远程 C-H 键硼化

• 发表时间: 2021
• 作者: Reyes;R. L.;Sato;M.;Iwai;T.;Suzuki;K.;Maeda;S.;and Sawamura;M.
• 通讯作者: M.

Encyclopedia of Reagents for Organic Synthesis

有机合成试剂百科全书

• 发表时间: 2020
• 作者: Reyes;R. L. and Sawamura;M.
• 通讯作者: M.

Enantioselective Desymmetrization of Cycloalkanes via Iridium-Catalyzed C(sp3)-H Borylation

通过铱催化的 C(sp3)-H 硼化对环烷烃进行对映选择性去对称化

• 发表时间: 2021
• 作者: Reyes;R. L.;Chong;S.-G.;Iwai;T.;and Sawamura;M.
• 通讯作者: M.

Modularly Designed Supramolecular Catalytic Assembly for the Strategic Enantioselective Borlyation of Remote C-H Bonds

模块化设计的超分子催化组件用于远程 C-H 键的战略对映选择性硼化反应

• 发表时间: 2021
• 作者: Reyes;R. L.
• 通讯作者: R. L.