Efficient synthesis of functionalized organozinc compounds by the direct insertion of zinc into organic iodides and bromides.
@article{Krasovskiy2006EfficientSO,
title={Efficient synthesis of functionalized organozinc compounds by the direct insertion of zinc into organic iodides and bromides.},
author={Arkady L. Krasovskiy and Vladimir Malakhov and Andrei Gavryushin and Paul Knochel},
journal={Angewandte Chemie},
year={2006},
volume={45 36},
pages={
6040-4
}
}Significance: Organozinc compounds are very useful intermediates in synthesis of complex organic molecules due to their high reactivity combined with an excellent tolerance of functional groups. So far, the direct insertion of commercial zinc dust into organic halides was limited only to alkyl iodides and tertiary bromides, which diminished its synthetic value. Herein, a new method, allowing the preparation of aryland hetarylzinc iodides, alkyland several arylzinc bromides by the direct…
298 Citations
Preparation of functionalized organoaluminiums by direct insertion of aluminium to unsaturated halides
- ChemistryNature Chemistry
- 2010
By adding catalytic amounts of selected metallic chlorides to aluminium powder in the presence of LiCl, aluminium powder inserts into various unsaturated iodides and bromides under mild conditions, and the utility of these organoaluminium reagents is demonstrated by their reaction with a wide variety of electrophilic coupling partners.
Preparation of aryl and heteroaryl indium(III) reagents by the direct insertion of indium in the presence of LiCl.
- ChemistryAngewandte Chemie
- 2008
A preparation of polyfunctional aryl and heteroaryl indium(III) reagents through the direct insertion of indium metal in the presence of LiCl into iodides 2 was reported, providing access to organoindium reagents containing a range of important and sensitive functional groups that are not compatible with organozinc reagents.
Strategies to prepare and use functionalized organometallic reagents.
- ChemistryThe Journal of organic chemistry
- 2014
Efficient and general preparations of zinc and magnesium organometallic reagents, as well as their most practical and useful reactions, are presented in this Perspective.
MgCl2-accelerated addition of functionalized organozinc reagents to aldehydes, ketones, and carbon dioxide.
- ChemistryAngewandte Chemie
- 2010
A practical and highly effective MgCl2-accelerated addition of various organozinc reagents to aldehydes and ketones as well as to CO2 under mild conditions is reported.
Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
- ChemistryChemistry
- 2019
Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross‐coupling or electrophilic substitution reactions.
Preparation of Polyfunctional Organozinc Halides by an InX3 - and LiCl-Catalyzed Zinc Insertion to Aryl and Heteroaryl Iodides and Bromides.
- ChemistryChemistry
- 2017
The use of a THF/DMPU (1:1) mixture shortens the reaction rates and allows the preparation of keto-substituted arylzinc reagents.
Preparation of polyfunctional arylmagnesium, arylzinc, and benzylic zinc reagents by using magnesium in the presence of LiCl.
- ChemistryChemistry
- 2009
The presence of LiCl considerably facilitates the insertion of magnesium into various aromatic and heterocyclic bromides and directing groups such as -OPiv, -OTs, -N(2)NR(2), or -OAc orient the zinc insertion to the ortho-position, while the reaction with Mg/LiCl/ZnCl leads to regioselective insertion into the para-carbon-bromine bond.
Preparation of functionalized organoindium reagents by means of magnesium insertion into organic halides in the presence of InCl3 at room temperature.
- Chemistry, BiologyChemistry
- 2013
The resulting organoindium reagents could be efficiently used as reagents in Pd-catalyzed cross-coupling reactions with a wide functional group tolerance.
Mild Negishi cross-coupling reactions catalyzed by acenaphthoimidazolylidene palladium complexes at low catalyst loadings.
- ChemistryThe Journal of organic chemistry
- 2013
The catalyst system displayed superiority in the construction of heterobiaryls through the coupling of heteroarylzinc reagents and heterocylic chloroarenes which were hardly accessible from the corresponding organoboron reagents by Suzuki-coupling reactions.
C60-Catalyzed Preparation of Aryl and Heteroaryl Magnesium and Zinc Reagents Using Mg/LiCl
- Chemistry, Biology
- 2015
The resulting organomagnesium and organozinc reagents efficiently underwent reactions with electrophiles, such as an aldehyde, an acid chloride, an allylic bromide, or an aryl iodide.
References
SHOWING 1-10 OF 23 REFERENCES
A new preparation of highly functionaized aromatic and heteroaromatic zinc and copper organometallics
- Chemistry
- 1990
Functionalized arylzinc compounds in ethereal solvent: direct synthesis from aryl iodides and zinc powder and application to Pd-catalyzed reaction with allylic halides.
- Chemistry, BiologyThe Journal of organic chemistry
- 2003
Pd(dba)(2) exhibited an outstanding efficient catalytic effect for the cross-coupling of these ethereal solutions of ArZnX with allylic halides to afford a variety of functionalized allylbenzenes in high yields.
The direct formation of functionalized alkyl(aryl)zinc halides by oxidative addition of highly reactive zinc with organic halides and their reactions with acid chlorides, .alpha.,.beta.-unsaturated ketones, and allylic, aryl, and vinyl halides
- Chemistry
- 1991
Highly reactive zinc, prepared by the lithium naphthalenide reduction of ZnCl 2 , readily undergoes oxidative addition to alkyl, aryl, and vinyl halides under mild conditions to generate the…
The in Situ-generated Nickel(0)-catalyzed Reaction of Aryl Halides with Potassium Iodide and Zinc Powder
- Chemistry
- 1980
The in situ-generated nickel(0) species, presumably atomic nickel, from nickel(II) salt and zinc powder has been proved to be an effective catalyst for the Finkelstein-type displacement reaction of…
Ortho-Phenylenedizinc(II) Compounds Ultrasound-Promoted Synthesis from o-Diiodobenzene and Zinc Powder and Its Synthetic Application
- Chemistry
- 1994
A facile and efficient synthetic procedure of o-phenylenedizinc(II) compound from o-diiodobenzene and zinc powder under the irradiation of ultrasound is reported. The compound was proved to be a…
New efficient preparation of functionalized arylzinc or thienylzinc compounds from aryl or thienyl chlorides using cobalt catalysis
- Chemistry, Biology
- 2005
A new chemical method is described for the preparation of aryl or thienyl zinc intermediates from their corresponding aromatic or thienyl chlorides in a mixture of acetonitrile-pyridine, using cobalt…
Ultrasound-Promoted Synthesis of Arylzinc Compounds Using Zinc Powder and Their Application to Palladium(0)-Catalyzed Synthesis of Multifunctional Biaryls
- Chemistry
- 1993
Arylzinc compounds containing electron-withdrawing groups such as CO2CH3, CON(CH3)2, CN, Br, Cl, or CF3 at ortho position were prepared readily by the ultrasound-promoted reaction of aryl iodides w...
1,1-Dimetallic reagents for the elaboration of stereoselectively di- or trisubstituted linear substrates.
- ChemistryAccounts of chemical research
- 2001
This work presents here some examples which lead to di- or polysubstituted linear substrates, of given geometry, where the organodimetallic obtained has been doubly protonated by water.
New progress in the cobalt-catalysed synthesis of aromatic organozinc compounds by reduction of aromatic halides by zinc dust
- Chemistry, Biology
- 2003
Preparation of cyclic alkenylmagnesium reagents via an iodine/magnesium exchange.
- Chemistry, BiologyChemical communications
- 2005
Remarkably, the mild conditions of the I/Mg-exchange tolerate the presence of sensitive diene functionalities and produces the corresponding alkenylmagnesium reagents under mild conditions.