ChemInform Abstract: Stereocontrolled Synthesis of Functionalized Cyclohexanes via the Lithium Amide-Mediated Rearrangement of a meso 4,5-Disubstituted Cyclohexene Oxide.

ChemInform ◽  
2010 ◽  
Vol 29 (14) ◽  
pp. no-no
Author(s):  
P. O'BRIEN ◽  
J. J. TOURNAYRE
Keyword(s):  
Cyclohexene Oxide ◽  
Lithium Amide ◽  
Stereocontrolled Synthesis

Diastereoselective epoxide rearrangements using lithium amide bases: first stereocontrolled synthesis of 4-deoxyconduritols

2000 ◽  
pp. 1521-1522 ◽  
Author(s):  
Alex Kee ◽  
Peter O’Brien ◽  
Christopher D. Pilgram ◽  
Simon T. Watson
Keyword(s):  
Lithium Amide ◽  
Stereocontrolled Synthesis

Solvent-induced stereospecific isomerization of an allylic alcohol to a homoallylic alcohol catalyzed by a chiral lithium amide

1998 ◽  
Vol 76 (6) ◽  
pp. 795-799 ◽  
Author(s):  
Per I Arvidsson ◽  
Maria Hansson ◽  
Agha Zul-Qarnain Khan ◽  
Per Ahlberg
Keyword(s):  
Proton Transfer ◽  
Diethyl Ether ◽  
Allylic Alcohol ◽  
Cyclohexene Oxide ◽  
Deuterium Labeling ◽  
Lithium Amide

Deprotonation of cyclohexene oxide, 1, by lithium (S)-2-(1-pyrrolidinylmethyl)pyrrolidide, 2-Li, on changing the solvent from tetrahydrofuran (THF) to, for example, 2,5-dimethyltetrahydrofuran (DMTHF) or diethyl ether (DEE) has been shown to yield, besides the lithium alkoxide of 2-cyclohexene-1-ol, 3-Li, the lithium alkoxide of the homoallylic alcohol 3-cyclohexene-1-ol, 4-Li. It was shown that compound 4-Li is formed from 3-Li. No such rearrangement has been observed in THF. We have now shown that the solvent-induced isomerization of the lithium alkoxide of (S)-3-methyl-2-cyclohexene-1-ol, (S)-5-Li, catalyzed by 2-Li to the lithium alkoxide of (S)-3-methyl-3-cyclohexene-1-ol, (S)-6-Li, is 100% stereospecific. Furthermore, deuterium-labeling experiments suggest that the rearrangement of the proton is close to 100% intramolecular.Key words: 1,3-proton transfer, chiral lithium amide, intramolecular, solvent-induced isomerization, stereospecific.

ChemInform Abstract: Diastereoselective Epoxide Rearrangements Using Lithium Amide Bases: First Stereocontrolled Synthesis of 4-Deoxyconduritols.

ChemInform ◽  
2000 ◽  
Vol 31 (49) ◽  
pp. no-no
Author(s):  
Alex Kee ◽  
Peter O'Brien ◽  
Christopher D. Pilgram ◽  
Simon T. Watson
Keyword(s):  
Lithium Amide ◽  
Stereocontrolled Synthesis
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