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CO 2 O 2 Transformation of Carbon Dioxide 郭郭 2009.10.31

Transformation of Carbon Dioxide

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Transformation of Carbon Dioxide. 郭昌 2009.10.31. Trend in CO 2 emissions from fossil fuel combustion. Global change in CO 2 emissions (2004-2005). Top-10 emitting countries in 2005. World CO2 emissions by sector. CO 2 EMISSIONS FROM FUEL COMBUSTION (2007 Edition). - PowerPoint PPT Presentation

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CO2 O2

Transformation of Carbon Dioxide

郭昌2009.10.31

Trend in CO2 emissions from fossil fuel combustion Global change in CO2 emissions (2004-2005)

Top-10 emitting countries in 2005 World CO2 emissions by sector

CO2 EMISSIONS FROM FUEL COMBUSTION (2007 Edition)

Typical Transformations of Carbon Dioxide

一般意义上来说,可以将 CO2 看成是碳酸酐,可以很好的与碱性物质发生反应,比如, CO2 与格式试剂在低温下就可以发生反应,同样也可以与水、醇盐、氨基等发生加成反应,生成相应的羧酸根。

CO2

O

O

A

B+

-O

AO

B

A BNucleophiles(H2O, ROM, R2NH, RMgX,....)

LnM

OY

X

O

LnM

OY

X

O

X Y

alkene, alkyne,diene,allene, O2.....

Ir, Rh, Ni,Nb, Rh, Fe, Pd, Mo,等金属都可以与CO2络合。

JACS. 1977, 99, 2391.JACS.1983, 105, 5914.

Chem. Ber. 1977, 110, 2213.

Organometal l i cs, 1994, 13, 407- 409

Chem. Commun. 1981, 1145.

JACS, 1985, 107, 2985JACS. 1984, 106, 2732-2733JACS. 1986, 108, 2286.Organometallics 1990,9, 1337

Inorg. Chem. 1992,31,4481.

O

Cu

CO

CH3

LL=

N NAr Ar

Ar=2,6-(i-Pr)2C6H3

Organometallics, 2004, 23, 1191-1193

CO2 与金属形成络合物

JACS, 2005, 127, 7294-7295

CO2 与金属形成晶体

Rh

P(tBu)2

P(tBu)2

H

Cl

KH / H2Rh

P(tBu)2

P(tBu)2

H

H

CO2 Rh

P(tBu)2

P(tBu)2

H

OCOH

Organometallics 1996, 15, 1839-1844Organometallics 1988, 7, 13-15

N

iPr2P PiPr2IrH

H

H

JACS, 2009, 131, 14168-14169

氢化

Noyori, Nature, 1994, 368, 231-234

超临界 CO2 应用

CO2 + H2 + HN(CH3)2

RuCl2[P(CH3)3]4

scCO2N O + H2O

JACS, 1994, 116, 8851-8852JACS, 1996, 118, 344-355

超临界 CO2 应用

CO2 形成五元金属杂环

R + CO2Ni(cod)2(1 equiv)

DBU(2 equiv),0oC

H+

COOHR

+ CO2Ni(cod)2(1 equiv)

DBU(2 equiv),0oC Ni OO

DBUDBU

D+

COOH

D (95% D)

RNi(cod)2

2 DBUR

NiDBU DBU

CO2

irreversible

R

Ni OO

DBUDBU

+

ONi

O

R DBU

DBUCOOH

R

kinetically favored

JOC, 1999, 64, 3975-3978

CO2, Ni(0)

ligand

Ni

O

O

R-M RCOOM

PhCO2, Ni(cod)2

DBU, THF, 0oC Ni OO

NiPh

PhO

O

Ph

Ph

COOH

COOH

+

hydrolysis Me2Zn

Ph

CO2Me

CO2Me

ArZn

CO2Me

Ph

Ph+

Ph

Ph

CO2Me

OOZnR

Ni

ROO

Ni

R2Zn

RZnOOC R

R=Me

MeOOC COOMe

R=Ph

JACS, 2001, 123, 2895-2896

OL, 2005, 7, 195-197

CO2 形成五元金属杂环

OL, 2003, 15, 2599-2601

R

R'

TiOiPr

OiPr

CO2

TiO

O

OiPrOiPr

R

R'

1,E+

2,H+

COOHR

R' E

EJOC, 2003, 1157-1171

CO2 形成 6 元金属杂环

R1 R1 + CO2

Ni(0)

Tertiary phosphine O

O

R1

R1

R1

R1

R1 R1

Ni(0)Ni

R1

R1

R1R1

Ni

O

O

R1 R1

R1

R1CO2

O

NiO R1

R1 R1

R1

O

O

R1

R1

R1

R1

BCSJ, 1980, 53, 3329-3333Macromolecules, 1993, 26, 4840-4844Macromolecules, 1995, 28, 1312-1315Macromolecules, 1995, 28, 1356-1359Macromolecules, 1994, 27, 1289-1290

R

R

(0)Ni

CO

OO

Ni

O

R

R

R R

ONi

R

R

R

RO

O

R

R

R

R

O

JACS, 2002, 124, 10008-10009

CO2 插入反应

Ps: Ni(acac)2=5%, Et2Zn=4.5 equiv

JACS, 2004, 126, 5956-5957

PhOO

+ CO2(1 atm)

cat(5 mol%)

NMP,100oC PhOOO

O

1 2

PhOO

+ M+PhO

OM+

X- OM

XPhO

CO2 O

XPhO

OM

O

PhOOO

O

CO2 + M+X- OX

O-

PhOO

PhO

OM

O

OX

PhOOO

O

JOC, 1993, 58, 6198-6202

与环氧形成五元环

Yield up to 100%

JACS, 2001, 123, 11498-11499

Al , Cr, Co, Zn, Sn, Ni, Ru, Cu, Mn, 等金属都可以催化该反应,离子液体,四级铵盐等也可以很好的催化该反应。

J. Mol. Catal. A: Chem. 2004, 210, 31.J. Mol. Catal. A: Chem. 2002, 186, 1.Organometallics 2004, 23, 924.J. Org. Chem. 2003, 68, 1559.J. Am. Chem. Soc. 2004, 126, 3732.Inorg. Chem. 2004, 43, 4315.BCSJ.1996, 69, 2885.New J. Chem. 2001, 25, 639.Chem. Commun.2003, 896.Tetrahedron Lett. 2004,45, 8307.J. Org. Chem. 2005, 70, 7882.Green Chem. 2004, 6, 613.Org. Lett. 2002, 4,2561.Org. Lett. 2002, 4,2561.Chem. Commun. 2003, 2042.Chem. Eur. J. 2006, 12, 1004.J. Mol. Catal. A: Chem.2005, 226, 199.Organometallics,, 2004, 23, 6025.

与环氧形成五元环

O

+ CO2

catalystO O

* *

O

X

orO

CO2+catalyst

OO

* *

O

X

CHO PCHCPO PPC

Coates, ACIE, 2004, 43, 6618-6639Darensbourg, Coord. Chem.Rev, 1996, 153, 155-174

CO2与环氧合成高聚物的反应中,五元碳酸酯是最常见的副产物。五元碳酸酯相对于高聚物来说,是热力学产物,可以通过以下几个途径提高高聚物的生成的比例:1,催化剂2,温度(温度越低,越有利高聚物的生成)3,CO2的压力4,环氧的浓度5,抑制解聚6,催化剂中有多个结合位点(双金属有利形成高聚物)一般来说,五元碳酸酯都是由金属醇盐进攻邻位的碳酸盐形成的。

与环氧形成高聚物

Zn, Cr, Al, Co, La, Mn, 等金属可以催化 CO2 形成高聚物。

Macromolecules 1995, 28, 7577.JACS. 2000, 122, 12487.JACS. 2005, 127, 3031.Macromolecules 2005, 38, 6251.ACIE. 2003, 42, 5484.JACS. 2005, 127,10869.ACIE. 2004, 43, 3574.JACS. 2006, 128, 1664.JACS. 2005,127, 14026.JACS. 2002, 124,6335.Macromolecules 2005, 38,4089.J. Polym. Sci., Part A: Polym.Chem. 2003, 41, 3549.

与环氧形成高聚物

CO2 和 N- 杂环丙烷的反应

HN

+ CO2

Bu4NX or M+X-

solventO NH

O

Bu4NX = Bu4NBr yield =95% M+X- = LiBr Yield= 74%

HN

+ CS2

THF, rt, 24hS NH

STBAB

yield = 94%

Tetrahedron letters, 2003, 44, 7889-7891

N

R+ CO2

solventO N

O

R

Ts

TsLiBr

Tetrahedron letters, 2004, 45, 1363-1365Org. Lett., 2004 .6,. 2301-2304

DBU 吸收 CO2

Tetrahedron, 2002,58, 3155-3158Tetrahedron letters, 2004, 45, 7073-7075

2R1R2NH + CO2

Ionic liquid

base,170oC R2R1N NR1R2

O

+ H2O

Angew. Chem. Int. Ed. 2003, 42, 3257 – 3260

利用 CO2 合成尿素及异氰酸酯

J. Org. Chem. 2001, 66, 1035-1037

利用 CO2 合成氨基甲酸酯

92%

RNH2 + CO2 + R'OH

Bu2SnO

Me2C(OR')2

200oC RHN OR'

O

Chem. Commun., 2001, 2238–2239

L

HN OMe

O

HN OMe

O

Yield=83% yield =49

利用 CO2 合成氨基甲酸酯

Green chem, 2004, 6, 524-525

NH2

NH2

+ CO2MeOH, 150oC

6hHN

NH

O

+ H2O

Green Chem, 2003, 5, 340-342

R NH2 +R1

OHR2 +

CuClCO2

NO

RO

R2R1

Ionic liquids

R1

OHR2 +

CuClCO2

OO

O

R2R1

Ionic liquids

JOC, 2004, 67, 16-21JOC, 2004, 69, 391-394JOC, 2005, 70, 7376-7380

R1

NHR3R2 + CO2

Pd(OAc)2

toluene, 50oCO

N

O

R2R1

R3

CO2 合成五元杂环

BCSJ, 1999, 72, 1063

JACS, 2003, 125, 4874-4881

CO2 合成五元杂环

利用 CO2 合成有机羧酸

OL, 2008, 10, 2681-2683

Yield up to 90%

TL, 2004, 45, 3485-3487

BO

O

+ CO2

[Rh(OH)(cod)]2 dppe, CsF

dioxane,60oCCOOH

LnRh Ar

LnRh(I)

ArB(OR)2

CO2insertion

ArLnRhO

O

ArO

OLnRh

ArB(OR)2

Ar(RO)2BO

O

JACS, 2006, 128, 8706-8707

R'R3Sn CO2

Pd(Ph3)4+

THF,70oCR'

O

O

R3Sn

major

R'O

O

R3Sn+

minor

PdSnR3

Pd SnR3

CO2O

O

Pd SnR3

SnR3

Pd(PPh3)4

Pd

O

O

R3Sn

JACS, 1997, 119, 5057-5058

利用 CO2 合成有机羧酸

Yield up to 50%

CL, 1995, 567-568

CO2 合成羧酸

Organometallics, 1994, 13, 4645-4647

catalyst, CO2

M=Li, Mg, BR2, ZnR

catalyst, CO2

This workAr-X

ArM

ArCOOH

CO2 直接合成羧酸

JACS , ASAP

CO2 芳基化

ONaCO2(加压)

OH

COONaH+

OH

COOH

ONa

CO2

络合

O-Na+

O

O

O

COONaH

OH

COONaH+OH

COOH

Kolbe-schmitt反应

JACS, 2002, 124, 11379-11391

CL, 2003, 43, 454-455

Yield= 20-34%

CL, 2002, 102-103

R1 + CO2 + X R2 XCuI

K2CO3

R1

O

O

O

O R2

n

Macromolecules, 1996, 29, 2694-2695

CO2 与炔烃形成高聚物

TMS

OTf+ +R'2NH CO2

KF(2 equiv)18-crown-6(2 equiv)

THF, 0oC

NR'2

COOH

R'2NH

CO2

R'2N

H

OC

O

-+

COO-

R'2N

H+

NR'2

COOH

OL, 2008, 10, 3485-3487

CO2 合成六元环

Bu3Sn

R

R

Cl+ + CO2

10% PdCl2(PhCN)2 20% PBu3

70oC, 48h

R

O

O

R

+ Bu3SnCl

Organometallics, 2000, 19, 1458-1460

基于 CO2 的串联反应

RCOOH + R1NH2 + R2CHO + R3NC R

O

R1

R2 HN

O

R3

R1NH2 + R2CHO R2 NR1

RCOOH

R3NC

N+R2 R1

H

C-

N+

R3

O-O

R

R O

O NHN

R2

R1

R3

O

NR

-O

R1

R2

NR3 H+

R N

O

R1

R2 HN

O

R3

R2NH2

R3CHOR3 N

R2

R1OH + CO2

O O-

O

R1

R4NC

N+R3 R2

H

C-

N+

R4

O-O

OR1

O O

O NHN

R3

R2

R4

R1

O N

O

R2

R3 HN

O

R4R1

R2NH2 R3CHOR1OH+CO2 ++ + R4NC O N

O

R2

R3 HN

O

R4R1

JOC, 1998, 63, 867-871

Ugi 反应

转化图

H2

HCOOHDMF

H2

O

RO

O

O

R

OR

*

R

O O

O

*n

R2R1N NR1R2

O

NH

O

O

R'ArRHN OR'

O

NH2

CN

NH

NH

O

O

NR'R

NO

R O

R'

NO

R O

R1

RCOOH

R

COOHR

R1

X R2 X

R1

O

O

O

O R2

n

NR'2

COOH

TMSTfO

Bu3Sn

RR

Cl

R

O

O

R

CO2