Iridium‐Catalyzed Enantioselective Allylic Substitutions of Racemic, Branched Trichloroacetimidates with Heteroatom Nucleophiles: Formation of Allylic C‐O, C‐N, and C‐S Bonds

2021 ◽  
Author(s):  
Hien M. Nguyen ◽  
Madhawee Arachchi
Keyword(s):  
Allylic Substitutions

Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account

1994 ◽  
Vol 59 (1) ◽  
pp. 1-74 ◽  
Author(s):  
Pavel Kočovský
Keyword(s):  
Transition Metals ◽  
Cyclopropane Ring ◽  
Allylic Substitutions ◽  
Recent Developments ◽  
Cardioactive Drug ◽  
Novel Method ◽  
Metal Catalyzed ◽  
Electrophilic Additions ◽  
Near Future ◽  
First Time

This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.

Novel Ferrocenyl Ligands with Planar and Central Chirality in Pd-Catalyzed Allylic Substitutions

1999 ◽  
Vol 1 (11) ◽  
pp. 1863-1866 ◽  
Author(s):  
Dieter Enders ◽  
René Peters ◽  
Jan Runsink ◽  
Jan W. Bats
Keyword(s):  
Allylic Substitutions ◽  
Ferrocenyl Ligands

C2-Symmetric bis-thioglycosides as new ligands for palladium-catalyzed allylic substitutions

2003 ◽  
Vol 44 (16) ◽  
pp. 3401-3404 ◽  
Author(s):  
Noureddine Khiar ◽  
Cristina S Araújo ◽  
Eleuterio Alvarez ◽  
Inmaculada Fernández
Keyword(s):  
Allylic Substitutions ◽  
Palladium Catalyzed

Metal-catalyzed regiodivergent organic reactions

2019 ◽  
Vol 48 (16) ◽  
pp. 4515-4618 ◽  
Author(s):  
Carmen Nájera ◽  
Irina P. Beletskaya ◽  
Miguel Yus
Keyword(s):  
Organic Reactions ◽  
Ch Activation ◽  
Allylic Substitutions ◽  
Metal Catalyzed

This review discusses metal-catalysed regiodivergent additions, allylic substitutions, CH-activation, cross-couplings and intra- or intermolecular cyclisations.

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