New Carbon-based Ligands for Hydroamination and olefin metathesis catalysts

用于加氢胺化和烯烃复分解催化剂的新型碳基配体

• 批准号: 8299498
• 负责人: GUY BERTRAND
• 金额: $ 38.66万
• 依托单位: UNIVERSITY OF CALIFORNIA, SAN DIEGO
• 依托单位国家: 美国
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-08-01 至 2014-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8299498
• 关键词: Academia; Address; Alkenes; Alkynes; Amines; Ammonia; Area; Attention; Behavior; Carbon; Catalysis; Chemicals; Collaborations; Complex; Coupling; Development; Electronics; Electrons; Environment; Family; Funding; Goals; Hand; Industry; Isomerism; Lead; Ligands; Metals; Modification; Nature; Nitrogen; Palladium; Phosphines; Phosphorus; Preparation; Process; Property; Reaction; Reactive Nitrogen Species; Reporting; Research; Ruthenium; Skeleton; Technology; Therapeutic; Transition Elements; Work; base; carbene; catalyst; design; electron donor; improved; metal complex; novel; propadiene; scaffold; success; tool

Efficient and selective preparation of organic molecules is critical for the synthesis of therapeutics. Many of the most proficient known processes depend on the availability of catalysts. One of the advantages of organometallic catalysis is the ability to tune the activity and selectivity through modification of the ligands around the metal center. Recently, major advances have been reported thanks to the use of electron-rich phosphines and cyclic diaminocarbenes. We have uncovered several novel families of stable carbenes, such as the cyclic (alkyl)(amino)carbenes and the diaminocyclopropenylidenes, which behave as even more electron-donating ligands. They have already allowed for improving known palladium and ruthenium catalyzed processes, and even for promoting new metal catalyzed reactions. The full catalytic potential of complexes bearing these carbene ligands will be investigated. In order to obtain even more robust and efficient transition-metal catalysts, novel types of carbon- based ligands, which surpass the electron donating properties imposed by any other ligands, will be prepared. Special attention will be drawn on families of ligands for which it will be possible to precisely tune the steric and electronic parameters. There is a high demand for technology to produce therapeutics in a pure enantiomeric form, thus optically active versions of our new ligands will be prepared. The studies will be focused on catalytic processes for which real difficulties remain, and on chemical transformations, which have not yet been achieved, but are of critical importance for building the skeleton of complex molecules. Cascade reactions that involves several reactants, yet a single catalyst, and which lead to biologically relevant heterocycles and to important synthons will be developed. To accelerate the widespread implementation of our ligands, we have already formalized a collaboration with Robert Grubbs at Caltech, and we are looking forward to further partnerships. The ultimate goal of this research effort is to find truly practical catalysts, and catalytic reactions, which will find applications in both industry and academia for the selective synthesis of biologically important compounds. )

有机分子的有效和选择性制备对于合成 治疗学许多最熟练的已知过程依赖于 催化剂的有机金属催化的优点之一是能够调节催化剂的活性。 活性和选择性，通过改性的配体周围的金属中心。 最近，由于使用富电子的 膦和环状二氨基卡宾。我们发现了几个新的家庭， 稳定的卡宾，如环状（烷基）（氨基）卡宾和 二氨基亚环丙烯基，其表现为甚至更多的供电子配体。 他们已经允许改进已知的钯和钌催化的 工艺，甚至用于促进新的金属催化反应。全面催化 将研究带有这些卡宾配体的络合物的潜力。为了 获得更强大和更有效的过渡金属催化剂，新型碳- 的配体，其超过了由任何其他配体施加的电子供给性质。 配体，将被制备。将特别注意配体的家族， 可以精确地调节空间和电子参数。存在高 需要技术来生产纯对映体形式的治疗剂，因此 将制备我们的新配体的光学活性形式。这些研究将集中在 对催化过程仍然存在真实的困难，以及对化学 这些变革尚未实现，但对实现 构建复杂分子的骨架。级联反应涉及几个 反应物，但单一的催化剂，并导致生物相关的杂环， 将开发重要的应用程序。为了加速广泛实施 我们的配体，我们已经正式与罗伯特·格拉布斯合作， 加州理工学院，我们期待着进一步的合作。这个项目的最终目标 研究工作的重点是找到真正实用的催化剂和催化反应， 在工业界和学术界的应用，用于选择性合成生物 重要的化合物。 )

项目成果

Transient palladadiphosphanylcarbenes: singlet carbenes with an "inverse" electronic configuration (p(pi)2 instead of sigma2) and unusual transannular metal-carbene interactions (piC-->Pd donation and sigmaPd-->C back-donation).

瞬态钯二膦基卡宾：具有“逆”电子构型（p(pi)2 而不是 sigma2）的单线态卡宾和不寻常的跨环金属卡宾相互作用（piC-->Pd 供体和 sigmaPd-->C 反供体）。

• DOI: 10.1021/ja066738j
• 发表时间: 2007
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Vignolle,Joan;Gornitzka,Heinz;Maron,Laurent;Schoeller,WolfgangW;Bourissou,Didier;Bertrand,Guy
• 通讯作者: Bertrand,Guy

A Stable (Amino)(Phosphino)Carbene as bidentate ligand for Palladium and Nickel Complexes: Synthesis, Structure, and Catalytic Activity.

稳定的（氨基）（膦基）卡宾作为钯和镍配合物的二齿配体：合成、结构和催化活性。

• DOI: 10.1016/j.jorganchem.2005.06.036
• 发表时间: 2005
• 期刊: Journal of organometallic chemistry
• 影响因子: 2.3
• 作者: Teuma,Emmanuelle;Lyon-Saunier,Céline;Gornitzka,Heinz;Mignani,Gérard;Baceiredo,Antoine;Bertrand,Guy
• 通讯作者: Bertrand,Guy

Stable P-heterocyclic carbenes: scope and limitations.

• DOI: 10.1002/asia.200600300
• 发表时间: 2007-01
• 期刊: Chemistry, an Asian journal
• 作者: Jason D. Masuda;David Martin;Céline Lyon-Saunier;A. Baceiredo;H. Gornitzka;B. Donnadieu;G. Bertrand

Gold-catalyzed intermolecular Markovnikov hydroamination of allenes with secondary amines.

• DOI: 10.1021/ol901418c
• 发表时间: 2009-08-06
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Zeng X;Soleilhavoup M;Bertrand G
• 通讯作者: Bertrand G

Mesoionic thiazol-5-ylidenes as ligands for transition metal complexes.

• DOI: 10.1039/c1cc14165a
• 发表时间: 2011-10-14
• 期刊: Chemical communications (Cambridge, England)
• 作者: Mendoza-Espinosa D;Ung G;Donnadieu B;Bertrand G
• 通讯作者: Bertrand G