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ACIE2011, 50, 3760.

JACS 2003, 126, 12179.

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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 + + ' '# #

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BN

ACIE 2009, 48,973.

JACS 2011, 133, 11508.

general review:

Can. J. Chem.2009, 87,8.

BN !

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13 A A9 90 0 3 3< <4 46 6@ @

1=:<?A903<46@

1=:<?(

≡

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H

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]

⁻

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₂

B

₁₀

H

₁₂

]

[C meta-

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]

[C para-

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.;>/7

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BNCT = Boron Neutron Capture Therapy

10B + n → [¹¹B] → ⁴He(a-ray) + ⁷Li

13 % % G G> >2 2 5 5A A6 67 7F F) )

4B?AE.G1;3E[CB₁₁H₁₂]⁻0(#1;3E,*+483E.'- (1)tert-Bu483E.!

ACIE 2004, 43, 2908.

(2)Wheland&@9B

3.530 Å 3.489 Å

d

_C

334.2 (SO

₂

)

C–CH₃ = 1.429(4)–1.459(4) Å ^{JACS 1972, 94, 2034.}

483E/" .

NMR,

JACS 2003, 125, 1796.

(3)4B?AE$(.$)

Science 2000, 289, 101.

JACS 2005, 127,7664.

JACS 2006, 128, 3160.

(4)<AFCEC₆₀.=D:E

13 8 8 \ \W WY YZ Z6 6C C

Boronic Acids Ed by Deniss G. Hall Wiley-VCH, 2011

WYZ6\(*CVJ60 ()7 A=?UYQZI(=6)

ML[XAC! KNPXD4:

! KNPXC"\'C/1

Nature 1995, 374, 345.

! KNPXBFG9

JACS 2008, 130, 11872.

'A.I>GA,#

SRTOX5@'C&E/1

3@+#$B-;%

)@<HG2

13 B B 9 9A A? ?= =: :@ @/ /

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)/22 +8(5

Al-Al/.'*0

"!65,&7 9A<A" #%61 .-4.$

13 - - ] ]X XF FO O+ +% % 1 1

Ishihara, K.

Lewis Acids in Organic Synthesis Yamamoto, H., Ed.

Wiley-VCH: Weinheim, 2000.

]IXTRX4SG#=!&'?*79 : 7@85;C

]EXQ\X

]CBS(Corey-Bakshi-Shibata))

Organic Syntheses, 1993, Coll. Vol. 8, 578.

JACS 1987, 109, 5551.

]Flustrated Lewis Pairs

"/<AB2< 7;2XFO+:

XFO>=:; D8C

ACIE 2010, 49, 46.

( -.D36:;5 FUZ[RPWX[ENWNZ@

$0#[EXKZ KPZD#8C

TVZ(BH₃)>,792C4 HJLMTYWNZ>%,

13 , , M MI I= =B B* *' ' . .

Makromol. Chem. 1969, 130, 210.

!M>F?AE6-K*$6

;(23+5 &FHGL

Organometallics 2011, 30, 3217.

!M*$08/3*>BCI6 -+5 &FHGL

MFriedel-Clafts<I?I

!M@DJ6%)#$

JACS 1988, 110, 2650.

*$"6FHGL 71:4/9

MAD: methylaluminium bis(2,6-di-tert-butyl- 4-methylphenoxide)

13 ! ! ; ;1 1/ /9 96 6. .8 8

http://www.chem-station.com/odos/2009/06/brown-brown-hydroboration.html

1/92+ &1/92+

1/9*840+5

*8,837:'

JACS, 1964, 86,3565.

1/92+

ACIEE 1985, 24, 878.

Can. J. Chem.1973, 51, 2098.

*8-08*840+5'

#

#

$

1/92+

1/92+

cat = Rh(PPh3)3Cl 0.05 mol%, 20 min, 83%

(Rh-B)%"

13

HOMO

Tetrahedron Lett. 2000, 41, 6821.

Chem. Lett. 2000, 29, 982.

J. Organomet. Chem. 2001, 625, 47.

ACIE2008, 47,5650. ACIE2009, 48,9735.

ACIE 2010, 49, 2041.

J. Org. Chem. 1994, 59, 6753.

J. Organomet. Chem. 1993, 462, 107.

Cy₃P·BH₂I LDBB

Cy₃P·BH₂^–Li⁺

Li^{+ –•}

LDBB =

ClSiMe₃

SiMe₃ BH₂ Cy₃P

N C N Dip Dip

BH₂I

LDBB/TMEDA THF

Li^{+ –•}

LDBB =

N C N Dip Dip

BH₂

N C N Dip Dip

BH₂ O

O Et O Et

O O Et Li

ACIE 2010, 49, 9166.

N B N Dip

Br

Dip N

B N Dip

Li

Dip N

B N

Dip Dip

Li

N B N Dip

H

Dip N

B N Dip

nBu

Dip N

B N Dip

CH

Dip OH Ph

Li THF

H₂O ⁿBuCl 1) PhCHO

2) H₂O Dip = 2,6-ⁱPr₂C₆H₃

OB

O B

O O

Ph Ph

O

+ ⁿBu₃P (11 mol%) CuOTf (10 mol%)

Ph Ph

O pinB

96%

CuCl, LiCl, KOAc

OB

O Cu•KCl

Cl pinB then, H₂O 53%

(B₂pin₂) then, H2O

Mn B Mn OC CO

OC CO

Li⁺(DME)₃ Mn

B Mn

COCO OCOC

Cl

Li

DME Mn

B Mn

COCO OCOC

Me MeI

DME KC₈

Et₂O B

Ph Ph

Ph Ph

Cl

N N Mes

Mes B

Ph Ph

Ph Ph

N N

Mes Mes

K MeI

Et₂O B

Ph Ph

Ph Ph

Me

N N Mes

Mes

Science2006, 314,113. ACIE2007, 46,6710. JACS2007, 129,9570. ACIE2008, 47,6606. JACS2008, 130,16069. Chem. Lett.2008, 37,802. JACS2009, 131,14162. JACS2010, 132,11449.

Chem. Commun.2011, 47,5888. ACIE2011, 50,920. Eur. J. Org. Chem.2011,3951. ACIE2014, 53, 6259. JACS2016, 138,3548. ACIE2016, 55,11426. ACIE2016, 55,12827.ACIE2017, 56,1658.

8

84 4 % % # #

84%#

NC N

Dip B Dip

Br BrBr Dip = 2,6-ⁱPr₂C₆H₃

KC₈

Et₂O B B

C C H

H N N

N N

Dip Dip

Dip

Dip B B

C C H

H N N

N N

Dip Dip

Dip

Dip H

+ H

JACS 2007, 129, 12412. JACS 2008, 130, 3298.

B=B 1.560(18) Å (cf. B–B ca. 1.75 Å)

NC

N B

ClCl

Li

THF B B

C

N C N

N N

λ_maxB=B 1.590(5) Å = 538 nm (ε 4100)

ACIE 2012, 51, 9931.

red color

84%# 0 +-(

84%# /

&-'2

N

NMg Mg N N

Mes Mes Mes

Mes

Pt

Br B

Et₃P Et₃P

B Dur

Dur

+ Br ^Et3P_Pt

Et3P

B B Dur

Dur

84%# .

Dur = 2,3,5,6-Me4C6H1 79:.Dur-B=B-Dur ( ) 12B-B )*,3

Nat. Chem. 2013, 5, 115.

B BMes PEt₃ Mes

Et₃P

Ar = 3,5-(CF₃)₂C₆H₃ BAr₄

B BMes PEt₃ Mes

Et₃P

BAr₄

ACIE 2014, 53, 5689.

84.")!

84%#

ESR

NC N

Dip B Dip BrBr Dip = 2,6-ⁱPr₂C₆H₃

THF CN

N Dip B Br Dip

Br Na

NC N

Dip B

Dip CNN Dip B

Dip

Science 2012, 336, 1420.

B=B 1.449(3) Å l_{max= 600 nm}

# 12$$576

NC B Dip

CN B

Dip

H₂

B B C C H

H

N Dip N

Dip

84%# .

Chem. Eur. J. 2016, 22, 17169.

+

7 7 & &e eZ Z1 1 - -n nf fg gi ik k

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H C

H H N

B

boryleneH carbene nitrene BH₃ CH₄ NH₃

8"KRTBVEfgik

Mn CO

OC SiMe₂Ph

B BCl NMe₂ Cl

Me₂N

Mn OC OC

Mn OC OC

B NMe₂

ACIE 1995, 34, 825.

5L-RTQ

2A2)J>/M

< !9I4@SVG>U

hY]L6HBVEfgik Cf. CAAC (cyclic alkyl(amino)carbene)

N C

Dip H₂

N C Dip

H H

Science 2011, 333, 610. Science 2007, 316, 439.

NHCI+OG01AFJ>EPK σabm!lπX\^c_m!A'CG ,1IQ C?U

N C Dip

BBr₃

CN Dip N B

C Dip H

KC₈ TfOHs N

C Dip N B

C Dip H H

TfO

hY]fgikHL3$

ACIE 2016, 55, 14464.

N C B N C N B B C

N C

B

CAAC CAAC

CAAC CAAC

NC Dip CAAC =

CAAC Br B

BrCN

KC₈ N

C N CAAC NCB

N N

8N6CG CE(L

[hdkLσ!Iπ!W.

eZ1Acj`kBVU

eZ1HhY]A3$ DU

N B B N

O O

Cl Ph

Ph Cl

KC₈ N C B C

B N O O

Ph

Ph

N B B N

O O

TfO Ph

Ph Me MeOTf

KfgikIhY]7!eZ1W#F

;!L

Nat. Commun. 2015, 6, 7340.

LeZ1AhY]=AhY]7

) ) F F< <! ! 1 16 68 8

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 toluene 25 °C, 24 h

85%

(1 bar) NDip

BN(SiMe₃)₂

H H NDip

HB H

N(SiMe₃)₂

K;AGJLN42H₂2)

B B

H₂

hexane B B

H H RT, 2 h

52%

(1 bar)

@GIN2B-B# 0H₂2HCB?A

B B S S

B B

S H₂ S

toluene RT, 1/4 h

73%

(1 bar) H

H

@GI:NDIBN@:E=N42H₂

B B

H

H 2Li⁺

H2

THF-d₈ 100 °C, 2 d

quant.

(1 bar)

B B

H

H 2Li⁺

H H

J. Am. Chem. Soc. 2019, 141, 6082.

%!42*

B(I)42)9"

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B(II)-7B(III)42) '/3B.K;A)/

B-B# +.H⁺9

B B

CH3

CH₃ 2Li⁺

H₂ (1 bar) (37 mol %) Ph Ph

N Ph

tBu

Ph Ph N

Ph

tBu

H

H H

H

H H H H

>MM?IN2(15,8

3 + + L LJ JK KG GI IE EH H. .= = $ $

(NH4)2[Ce(NO3)6]>

1-*:483

SmI2>1-(:483

EFK<708

<708

+="<708 +,<708

f-1-:;C>

+1":;C d-D6;0=9

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→

→ JKGIEH=EFK>

'#+AB?20=9 /)&D:B@50

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z‰‘oD/L45 +~Œ‡NHo

1H NMR‚‡(Ž„\)

doqya

Lsebmij_v JACS2001, 123,2466.

M9:*+zˆ“%

DU)91,2-

YRE.1II p199-

J. Organomet. Chem. 1985, 285, C21.

~Œ‡NH

YRE.1II p35-

MRIT$

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IJ’/'Z’"/? A RQ=€|}‘†{Œ{… 1992 ISBN 4061533444 1G+‘ƒ‰ˆMo@O

Chem. Rev. 2002, 102, 2187.

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RLilCeCl₃x4evdlkRCeCl₂aPKG

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