ChemInform Abstract: Nucleophilic Additions of Grignard Reagents to N-Benzyl-2,3-O-isopropylidene-D-glyceraldehyde Nitrone (BIGN). Synthesis of (2S,3R) and (2S,3S)-3-Phenylisoserine.

ChemInform ◽  
2010 ◽  
Vol 30 (4) ◽  
pp. no-no
Author(s):  
P. MERINO ◽  
E. CASTILLO ◽  
S. FRANCO ◽  
F. L. MERCHAN ◽  
T. TEJERO
Keyword(s):  
Grignard Reagents ◽  
Nucleophilic Additions

scholarly journals Water opens the door to organolithiums and Grignard reagents: exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans

2016 ◽  
Vol 7 (2) ◽  
pp. 1192-1199 ◽  
Author(s):  
Luciana Cicco ◽  
Stefania Sblendorio ◽  
Rosmara Mansueto ◽  
Filippo M. Perna ◽  
Antonio Salomone ◽  
...  
Keyword(s):  
Organometallic Compounds ◽  
Grignard Reagents ◽  
Nucleophilic Additions ◽  
Organolithium Reagents ◽  
Reaction Media

Grignard and organolithium reagents undergo smooth nucleophilic additions to γ-chloroketones “on water”.

Nucleophilic additions of Grignard reagents to N-benzyl-2,3-O-isopropylidene-D-glyceraldehyde nitrone (BIGN). Synthesis of (2S,3R) and (2S,3S)-3-phenylisoserine

Tetrahedron ◽  
1998 ◽  
Vol 54 (40) ◽  
pp. 12301-12322 ◽  
Author(s):  
Pedro Merino ◽  
Elena Castillo ◽  
Santiago Franco ◽  
Francisco L. Merchán ◽  
Tomas Tejero
Keyword(s):  
Grignard Reagents ◽  
Nucleophilic Additions

Preparations of 6-substituted 6H-Dibenzo[b,d]thiopyrans and their S-oxides through nucleophilic additions to 6H-dibenzo[b,d]thiopyran-6-one

1983 ◽  
Vol 36 (4) ◽  
pp. 795 ◽  
Author(s):  
DD Ridley ◽  
MA Smal
Keyword(s):  
Carbonyl Group ◽  
General Procedure ◽  
Grignard Reagents ◽  
Nucleophilic Additions ◽  
Reactions With Nucleophiles ◽  
Acid Labile

Methods for the preparations of 6-substituted 6H-dibenzo[b,d]thiopyrans and the corresponding S-oxides were explored. The most general procedure involved the addition of Grignard reagents to 6H-dibenzo[b,d]thiopyran-6-one, whereupon 6-substituted 6H-dibenzo[b,d]thiopyran-6-ols were formed. The carbonyl group in the thioester thus behaved like an isolated ketone in its reactions with nucleophiles. The resultant dibenzothiopyran-6-ols were acid-labile, and dehydration products underwent further modification in some instances. Oxidation of the olefins afforded stable S-oxides. The dianion formed by reduction of dibenzothiophen also offered routes to 6-substituted 6Hdibenzo[b,d]thiopyrans, but the reactions of this dianion were non-regioselective and thus were of limited use.

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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