%N ,( 2 16oec.chembio.nagoya-u.ac.jp/PDFs/2019_KU_MainGroup/MGC_05.pdf · ^y% j 2h. h3 ,9 "h. $^y%...
11
, ,( ( 2 216 ! ! - - =KD;<@M=KDA7H2 S-;IK=KC5L4G@232 JACS 1965, 87, 1353. =KDA7H6J@M9;>=KDA7H6J@ =KD;<@ =KDA7H Corey-ChaykovskyO4K?B@02/8F;<@ Corey-ChaykovskyO;IK1=KC5@+.* JACS 2010, 132, 1828. $Corey-ChaykovskyORh$0;IK=KC5@ ACIE 2001, 40, 1430. review: Acc. Chem. Res. 2004, 37, 611. Corey-ChaykovskyO;IK$ $O JACS 2005, 127, 3240. S C H H Me σ* SC Me S C H H O σ* SO Me Me JACS 1997, 119, 9913. Prof. Ellman@Yale Prof. Aggarwal@Bristol Prof. MacMillan@Princeton $(/ )# &2'/ :KE4A9L. %"N 5
Transcript of %N ,( 2 16oec.chembio.nagoya-u.ac.jp/PDFs/2019_KU_MainGroup/MGC_05.pdf · ^y% j 2h. h3 ,9 "h. $^y%...
16S-
JACS 1965, 87, 1353.
Corey-Chaykovsky
Corey-Chaykovsky
JACS 2010, 132, 1828.
Corey-Chaykovsky Rh
ACIE 2001, 40, 1430.review: Acc. Chem. Res. 2004, 37, 611.Corey-Chaykovsky
JACS 2005, 127, 3240.
S CHH
Me
σ*SCMe
S CHH
O
σ*SOMe
Me
JACS 1997, 119, 9913.
Prof. Ellman@Yale
Prof. Aggarwal@Bristol
Prof. MacMillan@Princeton
5
16
JACS 1997, 119, 1460.ACIE 1997, 36, 2223.
16
Org. Synth. Coll. Vol. 5: 1082.
16 6
ACIE 1996, 35, 2660.Org. Biomol. Chem. 2011, 9, 1347.
a,b-
( )
( )
S=O→
→
→( )
1616
JACS 1997, 119, 8592.
JACS 1989, 111, 5949.
JACS 1998, 120, 11096.
( )
http://murai-kun.cocolog-nifty.com/blog/
JACS 2004, 126, 16696.
JACS 2004, 126, 5968.
J. Chem. Soc., Chem. Commun.1975, 539.
JACS 1987, 109, 1587.
17
JACS 1994, 116, 2448.Chem. Commun. 1998, 927.
IBX, Dess-Martin periodinane
J. Org. Chem. 1983, 48, 4155.
Ac2O, AcOH
IBXOxone®
= 2KHSO5•KHSO4•K2SO4
Oxone®
Chem. Rev.1996,96, 1123.Chem. Rev. 2002, 102, 2523.Chem. Rev. 2008, 108, 5299.
JACS 2009, 131, 251.
a
Science 2014, 345, 291.Science 2010, 328, 1376.
Science 2011, 332, 448.
SN2
Yakugaku Zasshi 2009, 129, 321.
http://www.chem-station.com/blog/2011/05/c-h.html
HFIP
80 ℃ 80.5 ℃ 323 ℃
1552010
ISBN 4782706286
HIVLipitor® (Atorvastatin)
2011ISBN 4274503615
http://www.org-chem.org/yuuki/yuuki.html( )
http://blog.livedoor.jp/route408/
↔C-F
F > Cl > Br > ICl > F > Br > I
( )
Hammett( I p174-)
JACS 1985, 107, 4565.Cf. CF3OCF3C–F 1.319-1.327 ÅC–O 1.365-1.395 Å
Cf. CF2=OC–O 1.171 Å
JACS 2005, 127, 2050.C6F6
nO→s*CF
CF3O–
C–F 1.390-1.397 ÅC–O 1.227 Å
(F+ ) (F−)
Henri MoissanNobel Prize 1906
(kcal/mol)
F–F : 38Cl–Cl : 58H–F : 136H–Cl : 103
C–H : 98C–F : 116C–Cl : 81
Si–F : 139Si–Cl : 91
P–F : 117P–Cl : 76
2 CoF2 + F2 → 2 CoF3
C6H14 + 28 CoF3 → C6F14 + 14 HF + 28 CoF2
F2
CsF > RbF > KF >> NaF > LiFKF+18-crown-6, KF+CaF2, (n-Bu)4N+F−
[HF, HF-Py, SF4, Et2NSF3 (DAST)]
C–H C–F→
F2
Co
N2 F2
3 CH
( )1 F1 2
2 F1 2
Chem. Rev. 1996, 96, 1585.1993, 51, 232.
Chem. Rev. 1996, 96, 1585.1993, 51, 232.
C COOCl
FF Δ
Na CCl
FF
CO2 Cl:CF2
OC4H9F F
OC4H942%
R
Me3Si CH
O
CF2Br2P(NMe2)3
R
Me3Si CH
CF
FBr P(NMe2)3
CF2Br
3 F( )1 (CF3
−, CF3·, CF3+ )
2 3
( )
OK
CF3COOH+XeF2 CF3X CF3
C–H
JACS 2006, 128, 7134.
JACS 2009, 131, 7520.JACS 2009, 131, 3796.JACS 2008, 130, 10060.
JACS 2010, 132, 3793.
Science 2010, 328, 1679.Chem. Commun. 2009, 1909.
Pd
JACS 2010, 132, 3648.
C–H
Science 2009, 325, 1661.
ACIE 2000, 39, 4359. Synlett 2005, 991.
ACIE 2005, 44, 3703, 2005, 44, 3706, 2008, 47, 4157. JACS 2005, 127, 8826, 2011, 133, 1738.
Review: Nature 2011, 473, 470.
Pd(IV)C–F Pd(IV)
Pd(II)
CuCF3Pd(IV)Pd(II)
Ti F+ F+
Cu(III)
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