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TRANSCRIPT
14( )
4 14 (Si,Ge,Sn) 5 →5 →
( 1 )
Si–H C–H→lone pair Si
→ ( 2 p9 )
Acc. Chem. Res. 1981, 14, 246.
Si–F
TBAF: nBu4N+F−
tetra(n-butyl)ammonium fluorideJ. Am. Chem. Soc. 2005, 127, 2050.
Greene's Protective Groups in Organic
SynthesisP. G. M. Wuts
John Wiley & Sons, 2014ISBN: 1118057481
4
14
(a- )(b- )
14 ( 1 p21 )
14 1
LG ELhttp://www.chem-station.com/odos/2009/07/peterson-peterson-olefination.html
Peterson
JACS 1996, 118, 11974.Chem. Mater. 2001, 13, 2680.
( )
EL
14
thanks to ( )
JACS 2003, 125, 4962.
2
―
ISBN 978-4807913442
Chem. Comm. 2012, 48, 1308.
Suzuki, K.; Matsuo, T.; Hashizume, D.; Tamao, K.JACS 2011, 133, 19710.
JACS 2012, 134, 6500.
Dipp = 2,6-iPr2C6H3
14
Science 1981, 214, 1343.
Mes = 2,4,6-Me3C6H2
Si=Si
Si≡Si
Science 2004, 305, 1755.
JACS 2010, 132, 2546.
Si=C
JACS 1996, 118, 12228.
Ge=O
Nat. Chem. 2012, 4, 361.
p-p*
p-p*
CO2
Peterson
thanks to ( )
Si=O
Si
Ar Ar
ArAr
Ar =tBu
OMetBuN2O
Si
Ar Ar
ArAr
O
Angew. Chem. Int. Ed. 2019, 58, doi: 10.1002/anie.201905198.
14p p-p*
JACS 2007, 129, 7766.
(dismutational aromaticity)
Science 2010, 327, 564-566.
JACS 2005, 127, 9978.Science 1997, 275, 60.
Tetrahedron 2001, 57, 3645.
Angew. Chem. Int. Ed. 2019, 58, 7749.
1
Science 2010, 328, 339.
14
Si-C
Science 2002, 297, 825.
Science 1993, 260, 1917.Science 1993, 262, 402.
Ph3Si+ClO4−
JACS 1986, 108, 2482.
35Cl NMR Olah
Ph3C+ ClO4−
Ph3Si+ ClO4−
Ph3Si+ ClO4− + H2O
ClO4− Si
35Cl NMR
Br SiSi
Science 2008, 321, 1188.
iPr3Si+[CB11H6Br5]− Et3Si+B[C6F6]−
Mes3Si+[CB11HMe5Br5]−
Si CBtBu
tBu tBuSi CB
HtBu tBu
Si CBH
tBu HSi CBH
H HCB
pyramidalizedtrigonal
bipyramidal
Science 2019, 365, 168.CB = [CB11H6Br5]−
Si–Br 2.477(4), 2.770(4) Å
14
Pure Appl. Chem.1999, 71, 393.
Brook sila-Wittig
JACS 1997, 119, 233.
Acc. Chem. Res. 1974, 7, 77. +
X
JACS 1999, 121, 10231.
Wurtz
LiTHF2
(sila-Wittig )
C=Si
14
ACIEE 1993, 32, 1054. JACS 2003, 125, 13328.
vs.
Science 2011, 331, 1306.
X
→
14M–H 14
J. Org. Chem. 1991, 56, 678.
M–H (kJ/mol)14
14
ESR X
JACS 2002, 124, 9865. JACS 2002, 124, 15160.ACIE 2003, 42, 1143. JACS 2003, 125, 9250.
ACIE 2014, 53, 1324.
Si-HTCI Aldrich
nBu3SnH
14 ss(catenation)
14 s 14 s
s
JACS 2006, 128, 6800.Chem. Phys. Lett. 1992, 198, 400.
Me
Me
Me3Si
Si
SiSiMe3σSiSi
σ*SiSi
trans conformation
Me3Si
Si
Si
SiMe3
σSiSi
Me2
Me2 Me2 Me2
σ*SiC
gaushe conformation
UV,IRtrans red shift
transred shift
Si–Si
GC
15 3 3
→lone pair s
→ sp2
Phys. Rev. 1951, 81, 798.
P
William S. KnowlesNobel Prize 2001
15 3 3
NH3 NH sp2.90 lone pair sp2.37
PH3 PH sp3.83 lone pair sp0.95
154 (E = N, P, As, Sb, Bi)
4
E
Wittig Horner-Wadsworth-EmmonsWittig
(Z) (E)
→→
→→
II p37-
R' = R' =
( )
(E)Horner-Wadworth-Emmons
15
Org. Synth. 1984, 62, 158.
P=SeNMR 31P–77Se
J. Chem. Soc., Dalton Trans., 1982, 51.Dalton Trans. 2008, 650.
P=C
Dalton Trans. 2007, 5505Tetrahedron 2008, 64, 10945.
Ar = 4-MeOC6H4Mes* = 2,4,6-tBu3C6H2 JACS, 2002, 124, 10968.
Bi
JACS 2016, 138, 12787.
P=S Lawesson
15P=P
JACS 1998, 120, 433.Science 1997, 277, 78.
JACS 1981, 103, 4587.
31P NMR
XUV/vis
d
Bull. Chem. Soc. Jpn. 2007, 80, 1884.
dP 442.6, 471.2
31P NMRdP −59.0
ACIE 2016, 55, 12827.
NB
NDip Dip
P
NB
NDip Dip
PNB
NDip Dip
LiDip = 2,6-iPr2C6H3
nBuLiN
BNDip Dip
P
NB
NDip Dip
PnBu
Li(solv)n
stabilized by pπ-pπ interaction
NMR
15
Arbuzov
15 3 3
Science 2003, 302, 259.
( ) Wittig
ACIE 2009, 48, 6836.
16
(P=S, P=Se, P=Te)
ss-pp
Org. Biomol. Chem. 2009, 7, 1258.
pyrrole vs. phosphole
planar at N pyramidalized P
JACS 2006, 128, 983.
1234 J. Mater. Chem.
2009, 19, 3364.
n
n
J. Am. Chem. Soc.2017, 139, 10374.
LUMO
STED
lone pairLUMO
16 216 2
REH (E = O,S,Se,Te)O < S < Se < TeRE− O > S > Se > TeRE− O < S < Se < Te
→→RE· O < S < Se < Te
a- (14,15 )
N OO S,Se s*C-Se C-S→
16
16
→
EtSCH2CH2Cl >> EtOCH2CH2Cl
https://sites.google.com/site/fluordoublet/( )
S CHH
Ph
σ*SC
RSH : RSeH : RTeH :
RSR : RSeR : RTeR :
RSSR : RSeSeR : RTeTeR :
16 2a-
http://www.chem-station.com/odos/2009/07/13--ketone-synthesis-with-13-d.html
review: ACIEE 1979, 18, 239.
a- vs.Se-Li
FAMSO
review: http://www.tokyokasei.co.jp/kikou/bun/129dr.pdf
FAMSO ketene dithioacetal monoxide
JACS 2010, 132, 11838.Chem. Eur. J. 2012, 18, 12690.ACIE 2014, 53, 7510.ACIE 2018, 57, 14230
S C SO
H H
1) NaH2) RX3) H3O+
FAMSO(Formaldehyde Dimethyl Dithioacetal S-Oxide)
CO
HR
BnNMe3+OH–PhCHO
S C SO
CH Ph Tetrahedron Lett. 1971, 12, 3151.Tetrahedron Lett. 1972, 13, 1383.Bull. Chem. Soc. Jpn. 1979, 52, 2013.
RLi→Se-Li
RLi→Se-Li
R2NLi→Se a
16 2
reviews:Chem. Rev. 2004, 104, 4891.Chem. Rev. 2004, 104, 5085.JACS 1973, 95, 948.
Acta Polymerica 1997, 48, 379.
PEDOT/PSS : P3HT : p
ACIE 2007, 46, 4273.