Selective organic synthesis through generation and reactivity control of hyper-coordinate metal species

The development of new strategies for the preparation of chiral amines is an important objective in organic synthesis. In this Synpacts, we summarize our approach for catalytically accessing nucleophilic aminoalkyl metal species from 2-azadienes, and its application in generating a number of important but elusive chiral amine scaffolds. Reductive couplings with ketones and imines afford 1,2-amino tertiary alcohols and 1,2-diamines, respectively, whereas fluoroarylations of gem-difluoro-2-azadienes deliver α-trifluoromethylated benzylic amines.1 Introduction2 Background: Umpolung Strategies for Preparing Chiral Amines3 Background: 2-Azadienes4 Reductive Couplings of 2-Azadienes5 Fluoroarylations of gem-Difluoro-2-azadienes6 Summary and Outlook

Download Full-text

Application of Heterogeneous Catalysts for Organic Synthesis by Controlling the Oxidation State of Metal Species

Journal of Synthetic Organic Chemistry Japan ◽

10.5059/yukigoseikyokaishi.71.1307 ◽

2013 ◽

Vol 71 (12) ◽

pp. 1307-1308

Author(s):

Yuta Nishina

Keyword(s):

Organic Synthesis ◽

Oxidation State ◽

Heterogeneous Catalysts ◽

Metal Species

Download Full-text

Selective Double Addition Reaction of an E‒H Bond (E = Si, B) to a C≡N Triple Bond of Organonitriles

Molecules ◽

10.3390/molecules23112769 ◽

2018 ◽

Vol 23 (11) ◽

pp. 2769 ◽

Cited By ~ 6

Author(s):

Masumi Itazaki ◽

Hiroshi Nakazawa

Keyword(s):

Organic Synthesis ◽

Reaction Mechanisms ◽

Triple Bond ◽

Addition Reaction ◽

Catalytic Cycle ◽

Metal Species

The catalytic double hydrometalation such as hydrosilylation and hydroborylation of organonitriles has attracted considerable attention because the obtained products are widely used in organic synthesis and it is thought to be one of the effective methods for reduction of organonitriles. However, the examples of these reactions are quite limited to date. This paper summarizes the development of selective double hydrosilylation, double hydroborylation, and dihydroborylsilylation of organonitriles, including their reaction mechanisms and the role of the metal species in the catalytic cycle.

Download Full-text

ChemInform Abstract: Selective Organic Synthesis Through Generation and Reactivity Control of Hypercoordinate Metal Species

ChemInform ◽

10.1002/chin.200931258 ◽

2009 ◽

Vol 40 (31) ◽

Author(s):

Tamejiro Hiyama

Keyword(s):

Organic Synthesis ◽

Metal Species

Download Full-text

Production and STEM examination of controlled-size silver clusters

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100075488 ◽

1983 ◽

Vol 41 ◽

pp. 338-339

Author(s):

M. A. Listvan ◽

R. P. Andres

Keyword(s):

Cluster Size ◽

Metal Clusters ◽

Experimental Parameter ◽

Carbon Films ◽

Metal Species ◽

Silver Clusters ◽

Free Jet ◽

Size Dependent ◽

Cluster Properties ◽

Controllable Size

Knowledge of the function and structure of small metal clusters is one goal of research in catalysis. One important experimental parameter is cluster size. Ideally, one would like to produce metal clusters of regulated size in order to characterize size-dependent cluster properties.A source has been developed which is capable of producing microscopic metal clusters of controllable size (in the range 5-500 atoms) This source, the Multiple Expansion Cluster Source, with a Free Jet Deceleration Filter (MECS/FJDF) operates as follows. The bulk metal is heated in an oven to give controlled concentrations of monomer and dimer which were expanded sonically. These metal species were quenched and condensed in He and filtered to produce areosol particles of a controlled size as verified by mass spectrometer measurements. The clusters were caught on pre-mounted, clean carbon films. The grids were then transferred in air for microscopic examination. MECS/FJDF was used to produce two different sizes of silver clusters for this study: nominally Ag6 and Ag50.

Download Full-text