→

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

PDF

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