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Transition Metal-Catalyzed Chemistry in Water at Room Temperature

室温水中过渡金属催化的化学反应

基本信息

批准号：
8667466
负责人：
BRUCE H. LIPSHUTZ
金额：
$ 25.19万
依托单位：
UNIVERSITY OF CALIFORNIA SANTA BARBARA
依托单位国家：
美国
项目类别：
财政年份：
2009
资助国家：
美国
起止时间：
2009-08-15 至 2015-05-31
项目状态：
已结题

项目摘要

DESCRIPTION (provided by applicant): A new paradigm for Pd-catalyzed cross-couplings between alkyl and aryl halides in water at room temperature will be further developed. Reactive, highly water-sensitive sp3-based organozinc reagents can be generated in situ and used as coupling partners, protected from their aqueous surroundings by a micellar environment. A study on the use of alkyl bromides as a less costly alternative to iodides will be undertaken. This new micellar nanotechnology will be applied to related cross-couplings of stereo-defined alkenyl halides. Such couplings would be an especially attractive alternative to Suzuki-Miyaura couplings that normally require prior formation of boronic acids or the equivalent. The stereochemistry of the products resulting from these couplings in water relative to that seen in organic solvents will also be compared. Related couplings applied to heteroaromatic halides will be studied, given the importance of heterocycles to the pharmaceutical industry. Novel transition metal-catalyzed tandem processes will be developed, both reactions of in this sequence to be conducted in water at room temperature. Stille couplings involving organostannane intermediates will also be investigated as coupling partners in micellar media. The first cases of couplings using nickel catalysis will also be further investigated in reactions of alkenyl halides with in situ-generated organozinc halides. A newly designed, inexpensive yet "healthy" surfactant has been identified and will be developed that enables room temperature couplings for several name reactions to be done in water. Higher levels of conversion relative to those seen in previous studies can be achieved, and hence, better yields of cross-coupling products are to be expected. The secret to this success is based on proper engineering of particle size, which better accommodates the intended chemistry.

描述(由申请人提供)：将进一步开发室温下钯催化水中烷基和芳基卤化物之间的交叉偶联的新范例。反应性、高度水敏性的SP3基有机锌试剂可在现场生成并用作偶联伙伴，通过胶束环境保护其不受水环境的影响。将进行一项关于将烷基溴化物用作成本较低的碘化物替代品的研究。这一新的胶束纳米技术将被应用于立体定义的烯基卤化物的相关交叉偶联。这种联轴器将是铃木-宫仓联轴器的一种特别有吸引力的替代方案，后者通常需要事先形成硼酸或类似物。还将比较这些偶联产物在水中的立体化学与在有机溶剂中的立体化学。鉴于杂环化合物对制药工业的重要性，将研究应用于杂环卤化物的相关偶联。将开发新的过渡金属催化的串联过程，这两个反应都将在室温下在水中进行。涉及有机锡烷中间体的Stille偶联也将作为胶束介质中的偶联伙伴进行研究。使用镍催化偶联的第一个案例也将在烯基卤化物与原位生成的有机卤化锌的反应中进行进一步的研究。一种新设计的、廉价但“健康”的表面活性剂已经被确定，并将被开发出来，使几个著名反应的室温偶联能够在水中进行。与以前的研究相比，可以实现更高水平的转化率，因此，可以预期更好的交叉偶联产品的产量。这一成功的秘诀是基于适当的颗粒大小工程，这更好地适应了预期的化学成分。

项目成果

期刊论文数量（46）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Cross-couplings between benzylic and aryl halides "on water": synthesis of diarylmethanes.

“水上的苯并卤化物”与芳基卤化物之间的跨偶联：二丁香乙烷的合成。

DOI：
10.1039/b922280d
发表时间：
2010-01-28
期刊：
Chemical communications (Cambridge, England)
影响因子：
0
作者：
Duplais C;Krasovskiy A;Wattenberg A;Lipshutz BH
通讯作者：
Lipshutz BH

Organocatalysis in water at room temperature with in-flask catalyst recycling.

室温下在水中进行有机催化，并在烧瓶内回收催化剂。

DOI：
10.1021/ol203242r
发表时间：
2012-01-06
期刊：
Organic letters
影响因子：
5.2
作者：
Lipshutz BH;Ghorai S
通讯作者：
Ghorai S

Highly selective reactions of unbiased alkenyl halides and alkylzinc halides: Negishi-Plus couplings.

DOI：
10.1021/ol201307y
发表时间：
2011-08-05
期刊：
Organic letters
影响因子：
5.2
作者：
Krasovskiy A;Lipshutz BH
通讯作者：
Lipshutz BH

"Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

室温下水中的“点击”和烯烃复分解化学由可生物降解的胶束实现。

DOI：
10.1021/ed300893u
发表时间：
2013
期刊：
Journal of chemical education
影响因子：
3
作者：
Lipshutz,BruceH;Boskovic,Zarko;Crowe,ChristopherS;Davis,VictoriaK;Whittemore,HannahC;Vosburg,DavidA;Wenzel,AnnaG
通讯作者：
Wenzel,AnnaG

Zn-mediated, Pd-catalyzed cross-couplings in water at room temperature without prior formation of organozinc reagents.