Reactions of Norbornen-7-one with Organolithium Reagents

1971 ◽  
Vol 49 (13) ◽  
pp. 2223-2228 ◽  
Author(s):  
F. R. S. Clark ◽  
J. Warkentin
Keyword(s):  
Solvent Effects ◽  
Grignard Reagents ◽  
Organolithium Reagents

Alkyllithium reagents (RLi: R = methyl, n-butyl, t-butyl) add to norbornen-7-one either without stereochemical preference (R = n-butyl) or with syn attack favored. This addition selectivity is qualitatively the same as that shown by corresponding alkylmagnesium reagents but competition from reduction is much less important in the case of alkyllithium reagents.Phenyllithium and vinyllithium add preferentially from the anti face, although the corresponding Grignard reagents add selectively from the syn face. Possible causes of the stereoselectivities are considered. Solvent effects on the stereochemistry of addition are small.

Recent Advances in the Synthesis of Enantiomerically Enriched Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols through Addition of Organometallic Reagents to Carbonyl Compounds

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1855-1873
Author(s):  
Senthil Narayanaperumal ◽  
Ricardo S. Schwab ◽  
Wystan K. O. Teixeira ◽  
Danilo Yano de Albuquerque
Keyword(s):  
Carbonyl Compounds ◽  
Building Blocks ◽  
Short Review ◽  
Biological Properties ◽  
Enantioselective Synthesis ◽  
Grignard Reagents ◽  
Organometallic Reagents ◽  
Important Family ◽  
Organolithium Reagents ◽  
Organozinc Reagents

Enantiomerically enriched diaryl, aryl heteroaryl, and dihetero­aryl alcohols are an important family of compounds known for their biological properties. Moreover, these molecules are highly privileged scaffolds used as building blocks for the synthesis of pharmaceutically relevant products. This short review provides background on the enantioselective arylation and heteroarylation of carbonyl compounds, as well as, the most significant improvements in this field with special emphasis on the application of organometallic reagents.1 Introduction2 Background on the Enantioselective Synthesis of Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols3 Organozinc Reagents4 Organolithium Reagents5 Grignard Reagents6 Organoaluminum Reagents7 Organotitanium Reagents8 Organobismuth Reagents9 Miscellaneous10 Conclusion

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”.

Control of Diastereoselectivity by Solvent Effects in the Addition of Grignard Reagents to Enantiopuret-Butylsulfinimine:  Syntheses of the Stereoisomers of the Hydroxyl Derivatives of Sibutramine

2005 ◽  
Vol 7 (13) ◽  
pp. 2599-2602 ◽  
Author(s):  
Bruce Z. Lu ◽  
Chris Senanayake ◽  
Nansheng Li ◽  
Zhengxu Han ◽  
Roger P. Bakale ◽  
...  
Keyword(s):  
Solvent Effects ◽  
Grignard Reagents ◽  
Derivatives Of

scholarly journals Regio- and stereoselective ring openings of unsymmetrical oxatricyclo adducts

1997 ◽  
Vol 75 (6) ◽  
pp. 665-680 ◽  
Author(s):  
Simon Woo ◽  
Masood Parvez ◽  
Brian A. Keay
Keyword(s):  
Ring Opening ◽  
High Selectivity ◽  
Alder Reaction ◽  
Diels Alder ◽  
Grignard Reagents ◽  
Electronic Effects ◽  
Diels Alder Reaction ◽  
Ring Opening Reaction ◽  
Organolithium Reagents ◽  
Ring Opening Reactions

SN2′ ring-opening reactions of a number of substituted 11-oxatricyclo[6.2.1.01,6]undec-9-en-5-ones prepared via the intramolecular Diels–Alder reaction employing a furan diene (IMDAF) are reported. Primary, secondary, and tertiary organolithium reagents were capable of effecting the ring-opening reaction, while methyllithium required activation before any ring opening was observed. Hydride reagents, organocuprates, and Grignard reagents were generally ineffective. The ring-opening reaction was highly regio- and stereoselective for attack at C9syn to the bridging oxygen atom provided that C8 was not substituted. A highly stereoselective nucleophilic addition to the carbonyl group anti to the bridging oxygen was also observed. The high selectivity appears to be due to a combination of steric and electronic effects. Keywords: SN2′ reactions, oxatricyclo adducts, Diels–Alder reaction, ring opening.

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