scholarly journals An overview on the applications of ‘Doyle catalysts’ in asymmetric cyclopropanation, cyclopropenation and C-H insertion reactions

2000 ◽  
Vol 112 (3) ◽  
pp. 197-207 ◽  
Author(s):  
Thomas J. Colacot
Keyword(s):  
Insertion Reactions ◽  
Asymmetric Cyclopropanation

General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Chemical Space ◽  
Synthetic Approach ◽  
Asymmetric Cyclopropanation ◽  
Redox Active ◽  
Wide Range ◽  
Leaving Group ◽  
Stereoelectronic Properties ◽  
Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

Design and Characterization of Novel Dirhodium Coordination Polymers - The Impact of Ligand Size on Selectivity in Asymmetric Cyclopropanation

2021 ◽  
Author(s):  
Zhenzhong Li ◽  
Lorenz Roesler ◽  
Till Wissel ◽  
Hergen Breitzke ◽  
Kathrin Hofmann ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Ligand Exchange ◽  
Dicarboxylic Acids ◽  
Sem Images ◽  
Asymmetric Cyclopropanation ◽  
The Impact

Three chiral dirhodium coordination polymers Rh2-Ln (n=1-3) have been synthesized via ligand exchange between dirhodium trifluoroacetate Rh2(TFA)4 and differently sized chiral dicarboxylic acids derived from L-tert-leucine. SEM images indicate that...

scholarly journals Reply to “Comment on ‘Atomistic Mechanisms of Mg Insertion Reactions in Group XIV Anodes for Mg-Ion Batteries’”

2020 ◽  
Vol 12 (13) ◽  
pp. 14739-14740
Author(s):  
Mingchao Wang ◽  
Jodie A. Yuwono ◽  
Vallabh Vasudevan ◽  
Nick Birbilis ◽  
Nikhil V. Medhekar
Keyword(s):  
Insertion Reactions ◽  
Group Xiv

The chemistry of stabilized clusters

1982 ◽  
Vol 308 (1501) ◽  
pp. 27-34 ◽  
Keyword(s):  
Electron Donor ◽  
Organic Molecules ◽  
Metal Cluster ◽  
Organic Substrates ◽  
Insertion Reactions ◽  
Donor Ligand ◽  
Small Organic Molecules ◽  
Wide Range ◽  
Metal Metal ◽  
High Yields

Studies of the chemistry of metal cluster complexes and, in particular, their reactions with small organic molecules, have been confined to relatively few systems. Among the reasons for this are: (i) not many clusters are easily synthesized in high yields; (ii) their reactions often give a multitude of products that are difficult to separate and characterize; (iii) the conditions required to bring about reactions often lead to fragmentation of the cluster into lower nuclearity (often mononuclear) species. One cluster whose chemistry has been extensively studied is [Os 3 H 2 (CO) 10 ]. This can be synthesized in high yields from [Os 3 (CO) 12 ] + H 2 (Knox et al. 1975) and reacts readily under mild conditions with a wide range of electron-donor molecules by virtue of its coordinative unsaturation (Shapley et al. 1975; Deeming & Hasso 1976; Adams & Golembeski 1979). Formally, one may consider that a metal—metal double bond is present, which is reduced to a single bond on coordination of an additional two-electron donor ligand such as an organophosphine. The presence of metal—hydrogen bonds in this cluster and the cluster’s ability to coordinate organic substrates enable it to undergo a wide variety of insertion reactions, leading to products that may be regarded as intermediates in the reduction of organic molecules by clusters (Deeming & Hasso 1975; Keister & Shapley 1975).

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