Chiral Ligand ( Chiral Ligand (((RR,, R, RRRR))))--- … * No part of contents on this Internet Web...

N

N

P

P

Date: 02/08/2011

Appearance; Orange powder

m.p.; 102-103 oC

[α]22D; -54.3 (c 1.00, CHCl3)

((((R, RR, RR, RR, R))))----QuinoxP*QuinoxP*QuinoxP*QuinoxP* （R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline

This P-chiral ligand developed by Prof. Imamoto (Chiba Univ.) is stable in air and moisture with excellent enantio-selectivities.

Technical notes

1) Enantio-selective Hydrogenation

Chiral Ligand Chiral Ligand Chiral Ligand Chiral Ligand ((((R,R,R,R, RRRR))))----QuinoxP*QuinoxP*QuinoxP*QuinoxP*

NHAcO

OMe H2 (3atm), r.t.

[Rh(nbd)2]BF4(R,R)-QuinoxP* (1mol%)

∗∗∗∗

NHAcO

OMe

NHAc

H2 (3atm), r.t.

[Rh(nbd)2]BF4(R,R)-QuinoxP* (1mol%)

MeO

O

∗∗∗∗

NHAc

MeO

O

NHAc

H2 (3atm), r.t.

[Rh(nbd)2]BF4

(R,R)-Ad-QuinoxP* (1mol%)∗∗∗∗

NHAc

Conversion = 100 %Conversion = 100 %Conversion = 100 %Conversion = 100 % 99.2% ee99.2% ee99.2% ee99.2% ee ββββ----Amino AcidAmino AcidAmino AcidAmino Acid

Conversion = 100 %Conversion = 100 %Conversion = 100 %Conversion = 100 % 99.999.999.999.9% ee% ee% ee% ee αααα----Amino AcidAmino AcidAmino AcidAmino Acid

Conversion = 100 %Conversion = 100 %Conversion = 100 %Conversion = 100 % 99.999.999.999.9% ee% ee% ee% ee Chiral AmineChiral AmineChiral AmineChiral Amine

2) Asymmetric Addition of Boronic Acids to Cyclohexenone

3) Asymmetric Ring Opening

4) Enantioselective Intermolecular Hydroacylation

5) Enantioselective Allyl-Allyl Cross-Coupling

Reference;Reference;Reference;Reference;

1.1.1.1. J. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. Soc., 2005,., 2005,., 2005,., 2005, 127,127,127,127, 11934 11934 11934 11934----11935119351193511935.

2.2.2.2. J. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. Soc., 20., 20., 20., 2010101010,,,, 111132323232, , , , 5328532853285328----5329532953295329

3.3.3.3. J. Am. Chem. J. Am. Chem. J. Am. Chem. J. Am. Chem. SocSocSocSoc., 20., 20., 20., 2009090909,,,, 111131313131,,,, 12552125521255212552----12553125531255312553

4.4.4.4. J. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. SocJ. Am. Chem. Soc., 20., 20., 20., 2009090909,,,, 111131313131,,,, 11664116641166411664----11665116651166511665

5.5.5.5. AngewAngewAngewAngew. Chem. Int. Ed. Chem. Int. Ed. Chem. Int. Ed. Chem. Int. Ed. 2009, 2009, 2009, 2009, 48484848, 1, 1, 1, 1----5555

KOH, dioxane/H2O

(R,R)-QuinoxP* (3mol%)

O

+

B(OH)2[RhCl(C2H4)2]2

*

O

CH2Cl2, r.t.

(R,R)-QuinoxP* (5mol%)+

[PdCl2(cod)]

O Et2Zn

OH

Et

ASIA: Organic Chemicals Sales Dept. 11-1, 9-chome, Kameido, Koto-ku, Tokyo 136-8515, Japan Tel +81-3-3636-8077 Fax +81-3-3636-8132 E-mail : [email protected]

USA, EU: JCI USA, Inc. 1311 Mamaroneck Avenue, Suite 145, White Plains, NY 10605 Tel +1-914-761-6555 Fax +1-914-761-6940 E-mail : [email protected] www.nippon-chem.com

ConversionConversionConversionConversion = 93 = 93 = 93 = 93 % % % % 98.2% ee98.2% ee98.2% ee98.2% ee

ConversionConversionConversionConversion = 88 = 88 = 88 = 88 % % % % 97.6% ee97.6% ee97.6% ee97.6% ee

(CH2Cl)2, 80 C

+

Ph H

O

NPh2

O

Me5-10 mol %

[Rh(QuinoxP*)]BF4

oPh

O Me

NPh2

O

*

Conversion 99%, 98% ee

THF, 60 C

+

5 % Pd2(dba)3

10 % QuinoxP*

o

91% ee

OBoc

B(pin)

NOTICE:

* No part of contents on this Internet Web site may be reproduced in any form or by any means including

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* Nippon Chemical Industrial Co., Ltd. makes no commitment to updating or correcting any information that is

provided on this Web site.

* Though the information and statements on the Web site are believed to be reliable, Nippon Chemical Industrial

Co., Ltd. makes no representations or warranties as to the completeness or accuracy of any of this product

information.

* All the products need to be handled with care to ensure safety.

© 2011 Nippon Chemical Industrial Co., LTD. All Rights Reserved.

Date: 2/4/2010

P-Chiral Phosphine Ligand (R,R)-BenzP*

P

P

Me t-Bu

Met-Bu

Appearance: White crystal

m.p.: 125-126 ℃℃℃℃[αααα]24D: +223 (c 0.54, AcOEt)

(R,R)-BenzP* （（（（R,R)-1,2-Bis(tert-butylmethylphosphino)benzene

BenzP* is an electron-rich P-stereogenic bisphosphine ligand. Its rhodium complex

exhibited excellent enantioselectivities of up to 99.9% and high catalytic activity of

up to 10 000 h-1 TOF in asymmetric hydrogenations of various functionalized alkenes.

Technical notes

1) Asymmetric Hydrogenation of αααα-Dehydroamino Acids

MMMMeeeeOOOOHHHH,,,, rrrrttttRRRR1111

NNNNHHHHRRRR2222

CCCCOOOOOOOORRRR3333

RRRR1111

NNNNHHHHRRRR2222

CCCCOOOOOOOORRRR3333

HHHH2222 RRRRhhhh((((BBBBeeeennnnzzzzPPPP****))))((((ccccoooodddd))))SSSSbbbbFFFF6666

94.194.194.194.133333333200200200200MeMeMeMeCbzCbzCbzCbz2222----pyrrolylpyrrolylpyrrolylpyrrolyl8888

99.199.199.199.133333333200200200200MeMeMeMeCbzCbzCbzCbz2222----FurylFurylFurylFuryl7777

99.999.999.999.90.30.30.30.33333500500500500MeMeMeMeAcAcAcAc3333----MeOMeOMeOMeO----4444----AcOCAcOCAcOCAcOC6666HHHH33336666

99.499.499.499.40.70.70.70.733331,0001,0001,0001,000HHHHAcAcAcAcmmmm----FCFCFCFC6666HHHH44445555

99.599.599.599.50.50.50.50.533331,0001,0001,0001,000HHHHAcAcAcAcPhPhPhPh4444

99.899.899.899.85555555510,00010,00010,00010,000MeMeMeMeAcAcAcAcPhPhPhPh3333

99.999.999.999.90.30.30.30.333331,0001,0001,0001,000MeMeMeMeAcAcAcAcPhPhPhPh2222

99.999.999.999.91111555510,00010,00010,00010,000MeMeMeMeAcAcAcAcHHHH1111

eeeeeeee (%)(%)(%)(%)TimeTimeTimeTime(h)(h)(h)(h)

HHHH2222

((((atmatmatmatm))))S/CS/CS/CS/CRRRR3333RRRR2222RRRR1111entryentryentryentry

ASIA: Organic Chemicals Sales Dept.

11-1, 9 Chome, Kameido, Koto-Ku, Tokyo 136-8515

Tel+81-3-3636-8077

Fax+81-3-3636-8132

E-mail : [email protected]

USA, EU: JCI USA, Inc.

1311 Mamaroneck Ave, Suite 145 White Plains, NY 10605

Tel +1-914-761-6555

Fax +1-914-761-6940

E-mail : [email protected]

2) Asymmetric Hydrogenation of ββββ-Dehydroamino Acids

MMMMeeeeOOOOHHHH,,,, rrrrttttRRRR1111CCCCOOOOOOOORRRR2222

HHHH2222 RRRRhhhh((((BBBBeeeennnnzzzzPPPP****))))((((ccccoooodddd))))SSSSbbbbFFFF6666AAAAccccHHHHNNNN

RRRR1111CCCCOOOOOOOORRRR2222

AAAAccccHHHHNNNN

98.598.598.598.5222233331,0001,0001,0001,000EtEtEtEtpppp----MeOCMeOCMeOCMeOC6666HHHH4444ZZZZ9999

97.297.297.297.20.50.50.50.533331,0001,0001,0001,000MeMeMeMePhPhPhPhZZZZ8888

86.386.386.386.31212121233331,0001,0001,0001,000EtEtEtEtiiii----PrPrPrPrZZZZ7777

94.094.094.094.0333333331,0001,0001,0001,000EtEtEtEtnnnn----PrPrPrPrZZZZ6666

99.999.999.999.9444433331,0001,0001,0001,000EtEtEtEtnnnn----PrPrPrPrEEEE5555

97.997.997.997.92121212155555,0005,0005,0005,000MeMeMeMeMeMeMeMeZ/EZ/EZ/EZ/E 1:11:11:11:14444

98.798.798.798.70.80.80.80.833331,0001,0001,0001,000MeMeMeMeMeMeMeMeZ/EZ/EZ/EZ/E 1:11:11:11:13333

97.697.697.697.60.80.80.80.833331,0001,0001,0001,000MeMeMeMeMeMeMeMeZZZZ2222

99.699.699.699.60.80.80.80.833331,0001,0001,0001,000MeMeMeMeMeMeMeMeEEEE1111

eeeeeeee (%)(%)(%)(%)TimeTimeTimeTime(h)(h)(h)(h)

HHHH2222

((((atmatmatmatm))))S/CS/CS/CS/CRRRR2222RRRR1111entryentryentryentry

3) Asymmetric Hydrogenation of Other Functionalized Alkenes

MeOOCCOOMe

NHAc

O2NP

O

OMeOMe

O O

Ph

S/C 500 3 atm 97.2% ee S/C 1,000 3 atm 99.2% ee S/C 1,000 3 atm 97.6% ee

(S,S)-BenzP* is also commercially available.

Reference: Org. Lett. 2010, 12, 4400-4403.

NOTICE:





* Though the information and statements on the Web site are believed to be reliable, Nippon Chemical

Industrial Co., Ltd. makes no representations or warranties as to the completeness or accuracy of any of this

product information.


© 2011 Nippon Chemical Industrial Co., LTD. All Rights Reserved.

Date: 2/4/2010

(S)-MARUOKA CAT P-NB

P Br

CF3

CF3

CF3

CF3

(S)-MARUOKA CAT P-NB

(S)-4,4-Dibutyl-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4,5-dihydro-

3H-dinaphtho[2,1-c:1’,2’-e]phosphepinium Bromide

Specification

Purity ： 98.9 % (31P-NMR（202MHz, CDCl3）) Appearance: White powder

m.p.: 262 ℃℃℃℃ ~ 263 ℃℃℃℃F.W.: C46H38BrF12P=929.65

Optical purity： [α]27D; -29.0 (c 0.50, CHCl3)

(lit. [α]27D; -26.8 (c 0.50, CHCl3））

CAS# : 1110711-01-7

NOTICE:









Date: 2/4/2010

（（（（R)-MARUOKA CAT P-NB

P Br

CF3

CF3

CF3

CF3

(R)-MARUOKA CAT P-NB

(R)-4,4-Dibutyl-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4,5-dihydro-


Purity ： >99 % (31P-NMR（202MHz, CDCl3）)Appearance: White powder

m.p.: 262 ℃℃℃℃ ~ 263 ℃℃℃℃F.W.: C46H38BrF12P=929.65

Optical purity： [α]27D; +29.8 (c 0.50, CHCl3)

Specification

CAS# : Not available yet

NOTICE:









Date: 2/4/2010

(S)-MARUOKA CAT P-TB

P Br

CF3

CF3

CF3

CF3

(S)-MARUOKA CAT P-TB

(S)-4,4-Di-t-butyl-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4,5-dihydro-


Specification

Purity ： >99 % (31P-NMR（202MHz, CDCl3）) Appearance: White powder

m.p.: 202 ℃℃℃℃ ~ 203℃℃℃℃F.W.: C46H38BrF12P=929.65

Optical purity： [α]27D; +14.3 (c 0.50, CHCl3)


NOTICE:









Date: 2/4/2010

P Br

CF3

CF3

CF3

CF3

(R)-MARUOKA CAT P-TB

(R)-4,4-Di-t-butyl-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4,5-dihydro-


Specification

Purity ： >99 % (31P-NMR（202MHz, CDCl3）) Appearance: White powder

m.p.: 202 ℃℃℃℃ ~ 204 ℃℃℃℃F.W.: C46H38BrF12P=929.65

Optical purity： [α]27D; -13.8 (c 0.50, CHCl3)

(R)-MARUOKA CAT P-TB


NOTICE:









Chiral Ligand ( Chiral Ligand (((RR,, R, RRRR))))--- … * No part of contents on this Internet Web...

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