Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
基本信息
- 批准号:RGPIN-2014-05279
- 负责人:
- 金额:$ 2.33万
- 依托单位:
- 依托单位国家:加拿大
- 项目类别:Discovery Grants Program - Individual
- 财政年份:2017
- 资助国家:加拿大
- 起止时间:2017-01-01 至 2018-12-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
The aim of my research program is to develop novel transition-metal-free carbon-carbon (C-C) bond forming methodologies using organoboranes. The underlying theme of my proposal is an amphoteric reactivity of organoboranes. Boranes are electrophilic when neutral but nucleophilic when negatively charged. In situ generation of nucleophilic species from neutral boranes and their novel reactions are being discussed. C-C bond forming reactions involving organoboron compounds are usually associated with transition-metals that are expensive, toxic and often require the presence of sophisticated ligands. Boron is inexpensive and environmentally benign. Moreover, its low toxicity resulted in the incorporation of boron into pharmaceuticals. Proposed reactions provide “greener” alternative to the currently available protocols. The first section focuses on the development of novel C-C bond forming reactions using potassium organotrifluoroborate salts. Recently, we have discovered a single-step synthesis of ketones from acyl chlorides and trifluoroborates. We propose that in situ generated electrophilic difluoroborane interacts with a carbonyl functionality of the acyl chloride producing nucleophilic borates and electrophilic species. The reaction between newly formed nucleophilic borate and an electrophile affords propargyl ketones. Importantly, the reaction occurs in the absence of transition metals. Similarly, reactions of imines, isocyanates and aldehydes with trifluoroborates under the developed conditions are anticipated to form important functionalities such as amines, amides and alcohols respectively.The second section describes the opening of aziridinium ion with organoboronic acids and the application of the reaction to the synthesis of beta and gamma amino acids. To our knowledge, there are no literature examples of aziridinium ions reacting with organoborones. In this case, neutral boronic acids will be activated and directed to the aziridinium electrophilic center by the Lewis basic moiety present in the substrate. The establishment of stereocenters, which takes place at the early stage of the synthesis, relies on well-known epoxidation protocols. Subsequent reactions are stereospecific, which prevents epimerization of the chiral centers. Therefore, the enantiomeric purity of the starting epoxide will be translated to the final amino acid. The final section of my proposal focuses on the development of transition-metal-free reactions between gaseous carbon monoxide and organoboranes. This approach describes novel reactions based on the activation of neutral organoboranes with carbon monoxide. I propose efficient synthesis of acyl boronate esters and complex trifluroborates that are known to have great synthetic potential but difficult to prepare. In addition, novel bora-Brook rearrangements of acyl boronates are being described.Overall, outcomes of this research program will result in greater atom economy and will decrease the amount of toxic waste associated with metals in both academic and industrial settings. In addition, novel methodologies will ensure rapid access to diverse chiral molecules, which is crucial for the development of complex molecules and natural products. In summary, the proposed research program will have a significant impact on our understanding of the fundamental aspects of boron chemistry, which in turn will lead to the development of green reactions for the synthesis of compounds of biological and medicinal relevance. This program will serve as an excellent tool for the training of both graduate and undergraduate students.
我的研究计划的目的是开发新的过渡金属无碳-碳(C-C)键形成方法使用有机硼烷。我的提案的潜在主题是有机硼烷的两性反应性。硼烷中性时亲电,带负电时亲核。讨论了中性硼烷原位生成亲核物质及其新反应。涉及有机硼化合物的C-C键形成反应通常与过渡金属有关,这些过渡金属昂贵,有毒,通常需要复杂的配体存在。硼价格低廉,对环境无害。此外,它的低毒性导致硼掺入药物。拟议的反应为目前可用的协议提供了“更环保”的替代方案。第一部分重点介绍了使用有机三氟硼酸钾的新型C-C键形成反应的发展。最近,我们发现了一种由酰氯和三氟硼酸盐一步合成酮的方法。我们提出原位生成的亲电二氟硼烷与酰基氯的羰基官能团相互作用产生亲核硼酸盐和亲电物质。新形成的亲核硼酸盐和亲电试剂之间的反应产生丙炔酮。重要的是,反应发生在没有过渡金属的情况下。同样,在已开发的条件下,亚胺、异氰酸酯和醛类与三氟硼酸酯的反应预计将分别形成重要的官能团,如胺、酰胺和醇。第二节介绍了氮铱离子与有机硼酸的开孔反应及其在合成氨基酸中的应用。据我们所知,还没有文献记载氮铱离子与有机溴酮反应的例子。在这种情况下,中性硼酸将被底物中的路易斯碱部分激活并引导到氮铱亲电中心。立体中心的建立,发生在合成的早期阶段,依赖于众所周知的环氧化协议。随后的反应是立体特异性的,这阻止了手性中心的外映化。因此,起始环氧化物的对映体纯度将被翻译为最终氨基酸。我的建议的最后一部分集中在气态一氧化碳和有机硼烷之间的过渡金属无反应的发展。这种方法描述了基于中性有机硼烷与一氧化碳活化的新反应。我建议有效地合成酰基硼酸酯和复杂的三氟硼酸酯,这是已知的有很大的合成潜力,但很难制备。此外,还描述了酰基硼酸盐的新型bora-Brook重排。总的来说,这项研究计划的结果将导致更大的原子经济性,并将减少与学术和工业环境中金属相关的有毒废物的数量。此外,新的方法将确保快速获得不同的手性分子,这对于复杂分子和天然产物的开发至关重要。总之,拟议的研究计划将对我们对硼化学基本方面的理解产生重大影响,这反过来将导致合成具有生物和医学意义的化合物的绿色反应的发展。这个项目将成为培养研究生和本科生的一个很好的工具。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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Bolshan, Yuri其他文献
Synthesis, Optimization, and Evaluation of Novel Small Molecules as Antagonists of WDR5-MLL Interaction
- DOI:
10.1021/ml300467n - 发表时间:
2013-03-01 - 期刊:
- 影响因子:4.2
- 作者:
Bolshan, Yuri;Getlik, Matthaeus;Smil, David - 通讯作者:
Smil, David
Enamide synthesis by copper-catalyzed cross-coupling of amides and potassium alkenyltrifluoroborate salts
- DOI:
10.1002/anie.200704711 - 发表时间:
2008-01-01 - 期刊:
- 影响因子:16.6
- 作者:
Bolshan, Yuri;Batey, Robert A. - 通讯作者:
Batey, Robert A.
Bromination of codeine and its derivatives: Revisiting a 95 year old process
- DOI:
10.1016/j.tetlet.2020.152234 - 发表时间:
2020-08-20 - 期刊:
- 影响因子:1.8
- 作者:
Barmaki, Samira;Ali, Arlene;Bolshan, Yuri - 通讯作者:
Bolshan, Yuri
Bronsted Acid-Catalyzed Reactions of Trifluoroborate Salts with Benzhydryl Alcohols
- DOI:
10.1021/acs.joc.5b02273 - 发表时间:
2015-12-18 - 期刊:
- 影响因子:3.6
- 作者:
Fisher, Kayla M.;Bolshan, Yuri - 通讯作者:
Bolshan, Yuri
Copper-catalyzed cross-coupling of amides and potassium alkenyltrifluoroborate salts: a general approach to the synthesis of enamides
- DOI:
10.1016/j.tet.2010.03.076 - 发表时间:
2010-07-03 - 期刊:
- 影响因子:2.1
- 作者:
Bolshan, Yuri;Batey, Robert A. - 通讯作者:
Batey, Robert A.
Bolshan, Yuri的其他文献
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{{ truncateString('Bolshan, Yuri', 18)}}的其他基金
Development of novel catalytic methodologies
新型催化方法的开发
- 批准号:
RGPIN-2022-04022 - 财政年份:2022
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2021
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2020
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2019
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2018
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Development of non-covalent chemical probes for mu, delta and kappa opioid receptors
mu、delta 和 kappa 阿片受体非共价化学探针的开发
- 批准号:
500505-2016 - 财政年份:2017
- 资助金额:
$ 2.33万 - 项目类别:
Collaborative Research and Development Grants
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2016
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Development of non-covalent chemical probes for mu, delta and kappa opioid receptors
mu、delta 和 kappa 阿片受体非共价化学探针的开发
- 批准号:
500505-2016 - 财政年份:2016
- 资助金额:
$ 2.33万 - 项目类别:
Collaborative Research and Development Grants
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2015
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
Transition-metal-free reactions of organoboranes.
有机硼烷的无过渡金属反应。
- 批准号:
RGPIN-2014-05279 - 财政年份:2014
- 资助金额:
$ 2.33万 - 项目类别:
Discovery Grants Program - Individual
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