Catalytic C−C Activation/Functionalization of Ketones and Amides

酮和酰胺的催化 C→C 活化/功能化

• 批准号: 10669393
• 负责人: Guangbin Dong
• 金额: $ 33.43万
• 依托单位: UNIVERSITY OF CHICAGO
• 依托单位国家: 美国
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-30 至 2027-06-30
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/10669393
• 关键词: Amides; Carbon; Chemicals; Chemistry; Complex; Coupling; Funding; Goals; Hydrogen Bonding; Investigation; Ketones; Laboratories; Lactams; Mediating; Medicine; Methods; Modification; Molecular; Oxidation-Reduction; Reaction; Reagent; Research; Skeleton; Structure; Surface; System; Transition Elements; Work; analog; carbon skeleton; catalyst; deacylation; functional group; interest; novel; public health relevance; scaffold; skeletal; small molecule; success

Abstract: We are engaged in the systematic efforts to exploit catalytic carbon–carbon (C−C) bond activation for developing new, general and synthetically useful methods. Our objective, in the proposed funding period, is to focus on C−C activation and functionalization of ketones and amides, as they are easily accessible and widely found in feedstock chemicals. Through harnessing the power of transition-metal catalysts, sometimes assisted by an organic activator, a suite of new, selective, and efficient methods involving C−C activation of ketones and amides will be developed. Specifically, we will: (i) explore new C−C activation modes that allow rapid access to complex sp3-rich ring systems, (ii) enable a novel and broadly applicable cross-coupling reaction via deacylation of unstrained ketones, and (iii) allow selective activation of α-C−C bonds of unstrained amides. The research proposed is expected to offer an atom-economical approach for preparing novel complex sp3-rich molecular scaffolds from readily available substrates, which should help to access greater chemical space beyond the “flatland”. It is also expected to simplify synthesis through new strategies for bond disconnections and to enable skeletal editing of complex molecules under redox-neutral conditions, capitalizing on C−C activation/functionalization of ketones and amides.

摘要：我们致力于系统地开发催化碳-碳（C−C） 我们的目标是开发新的、通用的和综合有用的方法。 拟议的资助期将重点关注酮的 C−C 活化和功能化 酰胺，因为它们很容易获得并且广泛存在于原料化学品中。 利用过渡金属催化剂的力量，有时辅以有机活化剂， 涉及酮和酰胺的 C−C 活化的一系列新的、选择性的和有效的方法将 具体来说，我们将： (i) 探索新的 C−C 激活模式，以实现快速访问 对于复杂的富含 sp3 的环系统，(ii) 实现新颖且广泛适用的交叉偶联 通过未应变酮的脱酰化反应，并且 (iii) 允许选择性激活 α-C−C 键 所提出的研究预计将提供一种原子经济的方法。 用于从现成的底物中制备新型复杂的富含 sp3 的分子支架， 应该有助于进入“平地”之外更大的化学空间，也有望简化。 通过新的键断开策略进行合成并实现骨架编辑 氧化还原中性条件下的复杂分子，利用 C−C 酮和酰胺的活化/功能化。

项目成果

Intermolecular [5+2] Annulation between 1-Indanones and Internal Alkynes by Rhodium-Catalyzed C-C Activation.

通过铑催化的 C-C 活化，1-茚满酮和内部炔烃之间的分子间 [5 2] 环化。

• 发表时间: 2021-09-06
• 作者: Zhang, Rui;Xia, Ying;Dong, Guangbin
• 通讯作者: Dong, Guangbin

Orthogonal cross-coupling through intermolecular metathesis of unstrained C(aryl)-C(aryl) single bonds.

通过无张力的 C(芳基)-C(芳基) 单键的分子间复分解进行正交交叉偶联。

• 发表时间: 2021
• 影响因子: 21.8
• 作者: Zhu, Jun;Zhang, Rui;Dong, Guangbin
• 通讯作者: Dong, Guangbin

Rhodium-Catalyzed (4+1) Cycloaddition between Benzocyclobutenones and Styrene-Type Alkenes.

铑催化的苯并环丁烯酮和苯乙烯型烯烃之间的 (4 1) 环加成反应。

• 发表时间: 2022-05-23
• 作者: Ochi, Shusuke;Zhang, Zining;Xia, Ying;Dong, Guangbin
• 通讯作者: Dong, Guangbin

Transition metal-catalyzed C-C bond activation of four-membered cyclic ketones.

过渡金属催化四元环酮的C-C键活化。

• DOI: 10.1007/128_2014_545
• 发表时间: 2024-09-13
• 期刊: Topics in current chemistry
• 作者: Tao Xu;Alpay Dermenci;Guangbin Dong
• 通讯作者: Guangbin Dong

Direct activation of relatively unstrained carbon-carbon bonds in homogeneous systems.

均相系统中相对无张力的碳-碳键的直接活化。

• DOI: 10.1039/c4qo00053f
• 发表时间: 2014-07-01
• 期刊: Organic chemistry frontiers : an international journal of organic chemistry
• 作者: Dermenci A;Coe JW;Dong G
• 通讯作者: Dong G