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1,2vs.
3
1,2 aa1)
(X = COR, CO2R, CN, NO2, P(O)(OR)2, SOR, SO2R, BR2)2)
(X = OR, NR2)3)
(X = SiR3, SR, SeR)4)
(X = halogen, OSO2R, OR)
2) ( 1 >2 >3 )
4)
( )
CHCl3 KOHCCl2→
1,2
ISBN 9784815806064
ISBN 9784807907601
ACIE 2011, 50, 3760.
JACS 2003, 126, 12179.
→
4(Cb = CONiPr2)
S CH2O
O O
Me2S O+
95%
+
(homologation)
homologation
1,2
pp-s* (n-s* )p116
9 @−78℃PMDTA→
lone pair
( )
a:b= 36:64 (H2O)
(1-2 )
( )
Supporting Information
( 7 )
7
7
( 7 ) ( )
( )
3335
http://oec.chembio.nagoya-u.ac.jp/docs.html
Hicks, J.; Vasko, P.; Goicoechea, J. M.; Aldridge, S.
Reversible, Room-Temperature C—C Bond Activation of Benzene by an Isolable Metal Complex.J. Am. Chem. Soc. 2019, 141, 11000-11003.
13
BN
ACIE 2009, 48, 973.JACS 2011, 133, 11508.
general review:Can. J. Chem. 2009, 87, 8.
BN
13
≡
[B12H12]2− [CB11H12]− [C2B10H12]ortho-
[C2B10H12]meta-
[C2B10H12]para-
[C2B10H12] BNCT = Boron Neutron Capture Therapy10B + n → [11B] → 4He(a-ray) + 7Li
13[CB11H12]−
(1)tert-Bu
ACIE 2004, 43, 2908.
(2)Wheland
3.530 Å
3.489 Å
dC 334.2(SO2)
C–CH3 = 1.429(4)–1.459(4) Å JACS 1972, 94, 2034.
NMR
JACS 2003, 125, 1796.
(3) ( )
Science 2000, 289, 101.
JACS 2005, 127, 7664.JACS 2006, 128, 3160.
(4) C60
13
Boronic AcidsEd by Deniss G. Hall
Wiley-VCH, 2011
(= )
Nature 1995, 374, 345.
JACS 2008, 130, 11872.
13
Al-Al
13
Ishihara, K.Lewis Acids in Organic Synthesis
Yamamoto, H., Ed.Wiley-VCH: Weinheim, 2000.
CBS(Corey-Bakshi-Shibata)
Organic Syntheses, 1993, Coll. Vol. 8, 578.
JACS 1987, 109, 5551.
Flustrated Lewis Pairs
ACIE 2010, 49, 46.
(BH3)
13
Makromol. Chem. 1969, 130, 210.
Organometallics 2011, 30, 3217.
Friedel-Clafts
JACS 1988, 110, 2650.
MAD: methylaluminiumbis(2,6-di-tert-butyl-4-methylphenoxide)
13
http://www.chem-station.com/odos/2009/06/brown-brown-hydroboration.html
JACS, 1964, 86, 3565.ACIEE 1985, 24, 878.
Can. J. Chem. 1973, 51, 2098.
cat = Rh(PPh3)3Cl0.05 mol%, 20 min, 83%
Rh-B
13HOMO
Tetrahedron Lett. 2000, 41, 6821.Chem. Lett. 2000, 29, 982.
J. Organomet. Chem. 2001, 625, 47.
ACIE 2008, 47, 5650. ACIE 2009, 48, 9735.
ACIE 2010, 49, 2041.
J. Org. Chem. 1994, 59, 6753.J. Organomet. Chem. 1993, 462, 107.
Cy3P·BH2ILDBB
Cy3P·BH2–Li+
Li+–•
LDBB =
ClSiMe3 SiMe3BH2
Cy3P
NCN DipDip
BH2I
LDBB/TMEDA
THF
Li+–•
LDBB =
NCN DipDip
BH2
NCN DipDip
BH2
O
OOEt Et
O OEt
Li
ACIE 2010, 49, 9166.
NB
NDip
Br
Dip NB
NDip
Li
Dip NB
NDip Dip
Li
NB
NDip
H
Dip NB
NDipnBu
Dip NB
NDip
CH
Dip
OHPh
Li
THF
H2O nBuCl 1) PhCHO2) H2O
Dip = 2,6-iPr2C6H3
OB
OB
O
O
Ph Ph
O+
nBu3P (11 mol%)CuOTf (10 mol%)
Ph Ph
OpinB
96%
CuCl, LiCl, KOAc
OB
OCu•KCl
ClpinB
53%then, H2O
(B2pin2)then, H2O
Mn B MnOC CO
OC COLi+(DME)3
MnBMn
COCOOC
OC
Cl
Li
DMEMn
BMn
COCOOC
OC
Me
MeI
DMEKC8
Et2OB
Ph Ph
PhPhClN
NMes
Mes B
Ph Ph
PhPh
N NMes Mes
KMeI
Et2OB
Ph Ph
PhPhMe
NN
Mes
Mes
Science 2006, 314, 113. ACIE 2007, 46, 6710. JACS 2007, 129, 9570. ACIE 2008, 47, 6606. JACS 2008, 130, 16069. Chem. Lett. 2008, 37, 802. JACS 2009, 131, 14162. JACS 2010, 132, 11449.Chem. Commun. 2011, 47, 5888. ACIE 2011, 50, 920. Eur. J. Org. Chem. 2011, 3951. ACIE 2014, 53, 6259. JACS 2016, 138, 3548. ACIE 2016, 55, 11426. ACIE 2016, 55, 12827. ACIE 2017, 56, 1658.
NC
NDip
B
Dip
Br
BrBr
Dip = 2,6-iPr2C6H3
KC8
Et2OB B
C
HC
H
NN
NN
Dip
Dip
Dip
DipB B
C
HC
H
NN
NN
Dip
Dip
Dip
Dip HH
+
JACS 2007, 129, 12412. JACS 2008, 130, 3298.
B=B 1.560(18) Å(cf. B–B ca. 1.75 Å)
NC
NBClCl
Li
THFB B
C
CNN
NN
λmax = 538 nm (ε 4100)B=B 1.590(5) Å
ACIE 2012, 51, 9931.red color
N
NMg Mg
N
N
Mes
MesMes
Mes
PtBr BEt3P
Et3P
B
Dur
Dur
Br+ PtEt3P
Et3P
BBDur
Dur
Dur = 2,3,5,6-Me4C6H1 Dur-B=B-Dur ( )B-BNat. Chem. 2013, 5, 115.
B BMes
PEt3Mes
Et3P
Ar = 3,5-(CF3)2C6H3
BAr4B B
Mes
PEt3Mes
Et3P
BAr4
ACIE 2014, 53, 5689.
ESR
NC
NDip
B
DipBrBr
Dip = 2,6-iPr2C6H3
THF
NCN
Dip
B
DipBrBr
Na
NC
NDip
B
DipN
CN
Dip
B
Dip
Science 2012, 336, 1420.
B=B 1.449(3) Ålmax = 600 nm
NC B
DipN
CB
Dip
H2B B
C
HC
H
N
NDip
Dip
Chem. Eur. J. 2016, 22, 17169.
CHH
NHBHborylene nitrenecarbene
BH3 CH4 NH3MnCO
OC SiMe2Ph
B BCl
NMe2Cl
Me2N
MnCO
OC
MnCO
OC
BNMe2
ACIE 1995, 34, 825.
2
Cf. CAAC (cyclic alkyl(amino)carbene)
NCDip
H2 NCDip
H H
Science 2011, 333, 610. Science 2007, 316, 439.
NHCσ π
NCDip
BBr3
NC
Dip
BNC
Dip HKC8 TfOHs N
C
Dip
BNC
Dip H H
TfO
ACIE 2016, 55, 14464.
N CB
N
CB
NCB
N
CB
CAAC CAAC
CAACCAAC
NC
Dip
CAAC =
CAAC
BBrBr
CN
KC8
NC
N CAAC
BNC
NN
σ π
N
B
NB
OO
Cl Ph
Ph Cl
KC8 NC
BCN
B
OO
Ph
Ph
N
B
NB
OO
TfO Ph
PhMe
MeOTf
Nat. Commun. 2015, 6, 7340.
Angew. Chem. Int. Ed. 2016, 55, 14067.
Chem. Lett. 2017, 46, 1714.J. Am. Chem. Soc. 2017, 139, 2593.
Angew. Chem. Int. Ed. 2014, 53, 13159.
NDip
B N(SiMe3)2
H2
toluene25 °C, 24 h
85%
(1 bar) NDip
BN(SiMe3)2
HH N
Dip
BH
H
N(SiMe3)2
H2
BB
H2
hexaneB B
H
H
RT, 2 h52%
(1 bar)
B-B H2
B B
SS
B B
SSH2
tolueneRT, 1/4 h
73%
(1 bar) H
H
H2
B
B
H
H 2Li+H2
THF-d8100 °C, 2 d
quant.
(1 bar)
B
B
H
H 2Li+
H
H
J. Am. Chem. Soc. 2019, 141, 6082.
B(I)DFT
B(II) B(III)B
B-B H+
B
B
CH3
CH3 2Li+
H2 (1 bar)(37 mol %)Ph Ph
N
Ph
tBu
Ph Ph
N
Ph
tBu
H
H HH
H H
HH
3
(NH4)2[Ce(NO3)6]1SmI2 1
f dp→
→
3
D/L+1H NMR ( )
JACS 2001, 123, 2466.
1,2-
II p199-
J. Organomet. Chem. 1985, 285, C21.II p35-
MRI
1992ISBN 4061533444
Chem. Rev. 2002, 102, 2187.
Gd 1H NMRT1
La Li
RLi CeCl3 RCeCl2
1H