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15 16
Wurtz
PCl5 Dess-Martin periodinane
→
Sir Derek BartonNobel Prize
1969
Pure Appl. Chem. 1987, 59, 937.
(1,2,11,12 )
Victor GrignardNobel Prize1912
≡
Rieke
+ K
C8K(potassium graphite)
M*
Rieke Mg-anthracene THFMg
4 3
4 2
t-C4H9Li (pentane )
→→
UCLAt-C4H9Li
http://www.chem-station.com/blog/2009/01/-t.html
t-C4H9Li( Chem-Station)
p*
( )
p* 1
R M
dioxane Schlenk
Grignard
"turbo" Grignard reagent
The first report for turbo-Grignard reagent: Ren, H.; Krasovskiy, A.; Knochel, P., Org. Lett. 2004, 6, 4215-4217.reviews: (a) P. Knochel, A. Gavryushin, K. Brade, "Functionalized organomagnesium compounds: Synthesis and reactivity" in The
Chemistry of Organomagnesium Compounds, eds. Z. Rappoport, I. Marek, John Wiley & Sons, Chichester, 2008, p511.(b) Ila, H.; Baron, O.; Wagner, A. J.; Knochel, P., Chem. Commun. 2006, 583-593.
Prof. Paul Knochel
i-PrMgCl·LiCl turbo Grignard reagentLiCl Mg
→Cl Mg→LiCl ArX+Mg→ArMgXAngew. Chem. Int. Ed. 2008, 47, 6802-6806.
ArLi
THF (Me2N)3P=O
J . Am. Chem. Soc. 1986, 108, 2102-2103.
DME 5X
(DME)3
J . Am. Chem. Soc. 2007, 129, 10974-10975.
detected by 1H NMR
( )
R'M M (=M )Cs > Rb > K > Ba > Na > Ca > Li > Mg
web pKaEvans: http://www2.lsdiv.harvard.edu/labs/evans/pdf/evans_pKa_table.pdfReich: http://www.chem.wisc.edu/areas/reich/pkatable/Williams: http://research.chem.psu.edu/brpgroup/pKa_compilation.pdf
a-→
+TMEDA→
( )
LDA
Shapiro reaction ( Li )
superbase ( ) ortho-metalation ( )
Schlosser, M., Pure Appl. Chem. 1988, 60, 1627-1634.
n-BuLi t-BuOK
directing group ( )
(p-tol-SO2−)
Herbert C. BrownNobel Prize 1979
C-M
Science 2012, 335, 567-570.R = Me
Tl
Friedel-Crafts
C–Li = 2.31 Å, Li–Li = 2.68 ÅLi
Li
Li–C = 2.36 Å
CH3Li
NMR 6Li-7Li
Organometallics: A Concise IntroductionC. Elschenbroich, A. Salzer, Wiley-VCH, 1992
MeBr+2Li→MeLi-LiBrMeLi LiBr
LiBrLiBr free MeLi
RLi R(R = Et, n-Bu, t-Bu, Ph, R'C≡C)
4R6
CH3Li
4
DME (1,2-dimethoxyethane) TMEDA(N,N,N',N'-tetramethylethylenediamine)Li
RLi→
or
dd+dd− dd+
dd−
JACS 1993, 115, 11016.
dppf
Lithium Chemistry: A Theoretical and Experimental Overview
Eds by A.-M. Sapse, P. V. R. Schleyer; Wiley-Interscience, 1995
2 4 10
JACS 1985, 107, 1810.
NMR+
(p2 ) THF LDA4
J. Am. Chem. Soc. 1991, 113, 8187.
( )
NMRor X
X
XLi
a
Li
GrignardSchlenk 25Mg NMR
SchlenkACIEE 1984, 23, 534.
Be
J. Organomet. Chem. 1990, 393, 315.
WilhelmSchlenk
EtMgBrMgBr2
Et2Mg
6 (=12 )
Schlenk
http://www.sugiyama-gen.co.jp/products/rikagaku/index.htmlhttp://www.sugiyama-gen.co.jp/schlenk/index.html
The manipulation of air-sensitive compounds 2nd Ed.D.F. Shriver, M.A. Drezdzon, Wiley-Interscience, ISBN: 047186773X
: D.F. Shriver, M.A. Drezdzon, , , ,
- - , , ISBN 4758333014
20 mL
1000 mL
NMR tube joint( )
J-Young( )
Kontes, ChemGlass, Aldrich
NMR
2
J-Young
O
NMR tube
15/25 WilmadNMR tube
(¥3500/ )
+
( )
tBuLi + bipyridine
CaH2
( )
GrignardSchlenk MgX2
Mg
2RMgX
MeMgX > EtMgX >i-PrMgX > t-BuMgX
MeMgX < EtMgX <i-PrMgX < t-BuMgX