19
1,2"! vs. 3

1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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Page 1: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

1,2vs.

3

Page 2: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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→

Page 3: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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

Page 4: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

1,2

pp-s* (n-s* )p116

9 @−78℃PMDTA→

lone pair

( )

a:b= 36:64 (H2O)

Page 5: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

(1-2 )

( )

Supporting Information

( 7 )

7

7

( 7 ) ( )

( )

PDF

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.

Page 6: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

13

BN

ACIE 2009, 48, 973.JACS 2011, 133, 11508.

general review:Can. J. Chem. 2009, 87, 8.

BN

Page 7: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

13

[B12H12]2− [CB11H12]− [C2B10H12]ortho-

[C2B10H12]meta-

[C2B10H12]para-

[C2B10H12] BNCT = Boron Neutron Capture Therapy10B + n → [11B] → 4He(a-ray) + 7Li

Page 8: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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

Page 9: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

13

Boronic AcidsEd by Deniss G. Hall

Wiley-VCH, 2011

(= )

Nature 1995, 374, 345.

JACS 2008, 130, 11872.

Page 10: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

13

Al-Al

Page 11: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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)

Page 12: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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)

Page 13: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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

Page 14: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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.

Page 15: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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.

Page 16: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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.

Page 17: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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

Page 18: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

3

(NH4)2[Ce(NO3)6]1SmI2 1

f dp→

Page 19: 1,2oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_03...84 % # 84 % # N C N Dip B Dip Br Br Br Dip = 2,6-iPr2C6H3 KC8 Et2O B B C H C H N N N N Dip Dip Dip Dip B B C C H H N N

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