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

基本信息

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
项目类别：
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

项目摘要

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至关重要疗法。许多最熟练的已知过程取决于可用性催化剂。有机金属催化的优点之一是能够调整通过修改金属中心周围的配体的活性和选择性。最近，据报道，由于使用了电子丰富磷和循环二氨基碳烯。我们发现了几个新颖的家庭稳定的碳纤维，例如环状（烷基）（氨基）碳纤维和二氨基丙烷类乙烯烯，其表现为更多的含电子配体。他们已经允许改善已知的钯和芳族催化过程，甚至用于促进新金属催化的反应。完整的催化将研究带有这些卡宾配体的复合物的潜力。为了获得更强大，更有效的过渡金属催化剂，新型碳 - 基于基于其他任何其他人施加的电子捐赠特性的配体配体将准备。将特别注意配体的家庭可以精确调整空间和电子参数。有一个高对以纯对映体形式生产治疗剂的技术的需求，因此我们将准备新的配体的光学活性版本。研究将集中关于剩下真正困难的催化过程，以及化学转型尚未实现，但至关重要建立复杂分子的骨骼。涉及几个的级联反应反应剂，却是单个催化剂，并导致生物学相关的异环和将开发重要的合成子。加速广泛的实施在我们的配体中，我们已经正式与罗伯特·格鲁布斯（Robert Grubbs）合作加州理工学院，我们期待着进一步的合作伙伴关系。最终目标研究工作是找到真正实用的催化剂和催化反应，这将发现在生物学上选择性合成的行业和学术界的应用重要化合物。）

项目成果

期刊论文数量（57）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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

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

Stable P-heterocyclic carbenes: scope and limitations.

DOI：
10.1002/asia.200600300
发表时间：
2007-01
期刊：
Chemistry, an Asian journal
影响因子：
0
作者：
Jason D. Masuda;David Martin;Céline Lyon-Saunier;A. Baceiredo;H. Gornitzka;B. Donnadieu;G. Bertrand
通讯作者：
Jason D. Masuda;David Martin;Céline Lyon-Saunier;A. Baceiredo;H. Gornitzka;B. Donnadieu;G. Bertrand

Synthesis of a simplified version of stable bulky and rigid cyclic (alkyl)(amino)carbenes, and catalytic activity of the ensuing gold(I) complex in the three-component preparation of 1,2-dihydroquinoline derivatives.