Action of Grignard Reagents. VIII. Action of Organomagnesium and Lithium Compounds on Benzo-, Naphtho-(2',3')-oxazol-2-ones and their N-Substituted Derivatives

1955 ◽  
Vol 77 (19) ◽  
pp. 5127-5130 ◽  
Author(s):  
Ahmed Mustafa ◽  
Wafia Asker ◽  
Orkede Hassan Hishmat
Keyword(s):  
Grignard Reagents ◽  
Lithium Compounds

PREPARATION OF C14-LABELLED ACIDS FROM C14O2 AND ARYL LITHIUM COMPOUNDS

1959 ◽  
Vol 37 (12) ◽  
pp. 1439-1446 ◽  
Author(s):  
A. C. Neish
Keyword(s):  
Benzoic Acid ◽  
Barium Carbonate ◽  
Grignard Reagents ◽  
Similar Sequence ◽  
Butyl Lithium ◽  
Organolithium Compounds ◽  
Lithium Compounds

A simplified technique was developed for carbonation of Grignard reagents or organolithium compounds, with C14O2 generated from barium carbonate. 3,4-(Dibenzyloxy)-bromobenzene was treated with n-butyl lithium in ether and then with C14O2 to give 3,4-(dibenzyloxy)-benzoic acid-carboxyl-C14. The yield was 74% based on barium carbonate. 2,6-Dichlorobenzoic acid-carboxyl-C14 (yield 77%) and 3,5-dichlorobenzoic acid-carboxyl-C14 (yield 76%) were prepared from the corresponding dichlorobromobenzenes by a similar sequence of reactions. Attempts to synthesize 2,4- and 2,5-dichlorobenzoic acids by this route gave poor yields of unidentified acids, from which the expected products could not be isolated.

PREPARATION OF C14-LABELLED ACIDS FROM C14O2 AND ARYL LITHIUM COMPOUNDS

1959 ◽  
Vol 37 (1) ◽  
pp. 1439-1446
Author(s):  
A. C. Neish
Keyword(s):  
Benzoic Acid ◽  
Barium Carbonate ◽  
Grignard Reagents ◽  
Similar Sequence ◽  
Butyl Lithium ◽  
Organolithium Compounds ◽  
Lithium Compounds

A simplified technique was developed for carbonation of Grignard reagents or organolithium compounds, with C14O2 generated from barium carbonate. 3,4-(Dibenzyloxy)-bromobenzene was treated with n-butyl lithium in ether and then with C14O2 to give 3,4-(dibenzyloxy)-benzoic acid-carboxyl-C14. The yield was 74% based on barium carbonate. 2,6-Dichlorobenzoic acid-carboxyl-C14 (yield 77%) and 3,5-dichlorobenzoic acid-carboxyl-C14 (yield 76%) were prepared from the corresponding dichlorobromobenzenes by a similar sequence of reactions. Attempts to synthesize 2,4- and 2,5-dichlorobenzoic acids by this route gave poor yields of unidentified acids, from which the expected products could not be isolated.

Fe-Catalyzed Conjunctive Cross-Couplings of Unactivated Alkenes with Grignard Reagents

2020 ◽  
Author(s):  
Lei Liu ◽  
Wes Lee ◽  
Cassandra R. Youshaw ◽  
Mingbin Yuan ◽  
Michael B. Geherty ◽  
...  
Keyword(s):  
Functional Groups ◽  
Cross Coupling ◽  
Alkyl Halides ◽  
Grignard Reagents ◽  
Turnover Frequency ◽  
Diverse Range ◽  
Cascade Cyclization ◽  
Radical Cascade

The first iron-catalyzed three-component cross-coupling of unactivated olefins with alkyl halides and Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles, alkyl halides, and unactivated olefins bearing diverse functional groups to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C-C bonds.

Design and Development of Fe-Catalyzed Intra- and Intermolecular Carbofunctionalization of Vinyl Cyclopropanes

2019 ◽  
Author(s):  
Lei Liu ◽  
Wes Lee ◽  
Mingbin Yuan ◽  
Chris Acha ◽  
Michael B. Geherty ◽  
...  
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Alkyl Halides ◽  
Grignard Reagents ◽  
Mechanistic Studies ◽  
Radical Intermediates ◽  
Design And Implementation ◽  
Solvent Cage ◽  
Radical Cascade ◽  
Radical Processes

Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of the alkyl radical intermediates out of the solvent cage to participate in an intra- or -intermolecular radical cascade with the VCP followed by re-entering the Fe radical cross-coupling cycle to undergo selective C(sp2)-C(sp3) bond formation. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.

Alkyl 1-[2-(oxido anion)-, 3-, 4-, 5-alkyl substituted]phenyl ketyl radicals

1979 ◽  
Vol 44 (6) ◽  
pp. 1731-1741 ◽  
Author(s):  
Andrej Staško ◽  
Ľubomír Malík ◽  
Alexander Tkáč ◽  
Vladimír Adamčík ◽  
Eva Maťašová
Keyword(s):  
Electron Donor ◽  
Unpaired Electron ◽  
Grignard Reagents ◽  
Slight Effect ◽  
Benzene Nucleus ◽  
Alkyl Groups ◽  
Splitting Constant

Reactions of R2,R3-alkyl substituted 2-hydroxybenzenecarboxylic acids 2-HO-C6H2R2-COOH with Grignard reagents R1MgBr in the presence of nickel give stable aryl alkyl ketyl radicals 2-O--R2-, R3-C6H2-CO--R1 where R1 = CH3, C2H5, C2D5, n-C3H7 and R2,R3 = CH3, C2H5, i-C3H7, t-C4H9. The β protons of ketyl group are equivalent (splitting constant 1.25 mT) and non-equivalent (splitting constants within 0.5 to 1.5 mT) for R1 = methyl and other alkyl groups, respectively. Interaction of the γ protons with the unpaired electron was only observed in the case of R1 = n-propyl (splitting constants about 0.07 mT). The substituents R1 have but slight effect on values of splitting constants of the protons in R2,R3 and vice versa. Also splitting constants of the benzene nucleus (a4H = 0.55 mT, a6H = 0.44 mT) are only slightly affected by the substituents R1,R2,R3, which indicates dominant electron-donor effect of the oxido-anion group eliminating the relatively smaller contributions of the alkyl substituents.

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