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Archives for: January 2009

01/28/09

Congratulations Alfred Bader for the Pittcon Heritage Award!

01:55:37 pm, Categories: Asymmetric Synthesis  

The 2009 Pittcon Heritage Award will be presented to Alfred R. Bader, Founder of Aldrich Chemical Company, owner of Alfred Bader Fine Arts. The award will be presented in the Opening Session, which begins at 4:30 p.m. on March 8 at the Pittcon Conference, taking place in Chicago from March 8-13, 2009.

This award recognizes outstanding individuals whose entrepreneurial careers shaped the instrumentation and laboratory supplies community, inspired achievement, promoted public understanding of the modern instrumentation sciences, and highlighted the role of analytical chemistry in world economies.
Alfred Bader established the Aldrich Chemical Company, later the Sigma-Aldrich Corporation, as one of the world’s leading suppliers of research chemicals. These research chemicals are essential tools for chemists of all kinds, used as key reagents and starting materials. During Bader’s long tenure at the firm, from 1951 to 1991, he oversaw the assembly of a huge library of rare chemicals—numbering nearly 50,000—in addition to thousands of more commonly used chemicals. The company’s annual catalog, which featured a red “A” on the binding and a reproduction of fine art on the cover, became widely known as “Big Red” and was often used as a reference for its physical data and structural information.

http://www.chemheritage.org/events/event-nav2-pittcon.html

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01/25/09

Brønsted Acid Catalysis of the Mukaiyama–Mannich Reaction of Aldimines with Vinylketene Silyl N,O-Acetals

09:47:18 pm, Categories: Catalysis  

Written by: Dr. Sharbil J. Firsan

Professor Schneider and co-workers of the University of Leipzig have recently reported a regio- and enantioselective protocol for converting vinylketene silyl N,O-acetals into delta-amino-alpha,beta-unsaturated amides in generally good yields.  This version of the Mukaiyama–Mannich reaction relies on the use of a BINOL-based phosphoric acid as a Brønsted acid catalyst and is carried out under mild conditions (–30 oC) and low catalyst loadings (1 mol %).  The transformation can also be carried out with the same efficiency and enantioselectivity as a three-component reaction by using an aldehyde, amine, and silyl dienolate—thus avoiding the synthesis of the imine intermediate.  One limitation of this protocol is that aliphatic aldimines decompose under the reaction conditions.

 


(1) Giera, D. S.; Sickert, M.; Schneider, C. Org. Lett. 2008, 10, 4259.  (2) For a recent review on related Brønsted acid catalysts, see Adair, G.; Mukherjee, S.; List, B. Aldrichimica Acta 2008, 41, 31.

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01/13/09

Ni Catalyzed Borylation and Cross-Coupling of Aryl Halides

06:42:58 pm, Categories: Cross-Coupling  

Written by William Sommer, PhD.

Rosen et al. devised a new way to synthesize aryl neopentylglycolborane using [(diphenylphosphino)propane]dichloronickel as a catalyst (Scheme 1). The resulting aryl is then cross-coupled with a variety of aryl halides using  [(diphenylphosphino)etane]dichloronickel as a catalyst (Scheme 2). This method allows for the synthesis of a variety of functional biaryls using inexpensive catalysts. It was noted that 10 mol% of the ligand, (diphenylphosphino)propane was needed to increase the yields of the borylation reaction. It is interesting to note that it was also the case for the coupling reaction where 10 mol% of (diphenylphosphino)ethane was needed. Overall, the authors describe an interesting method to get access to a variety of coupling reagents in a one pot synthesis followed by an efficient coupling of this aryl with another aryl.

Scheme 1
 
Scheme 2
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