M R R

d-

d+

R d+ R
TIPO FISCHER

R d- R
TIPO SCHROCK

N M-

CARBENOS LIBRES

CARBENOS NHC

Grupo 6 ( Cr, Mo, W), bajo estado de oxidacin Carbono carbnico electroflico Heterotomos como sustituyentes Estabilizados por ligantes aceptores Estado energtico singulete

OC OC

CO M CO

CO CO

R-Li

OC CO O OC M C R OC CO

Li

Me 4NBr

OC CO O OC M C R OC CO

NMe 4

Reactivo de Meerwein

Me 3O +

BF 4-

Slido amarillo estable

OC CO OC M OC CO

OMe C R

OC CO OC M OC CO

OMe C R

OC OC

CO M CO

CO CO

R-Li

OC CO O OC M C R OC CO

Li

Me 4NBr

OC CO O OC M C R OC CO

NMe4

COCl -40C

O O (OC) 5 Cr C R aciloxicarbeno

-20C, rapido R`OH

OR` (OC) 5 Cr C R

COOH

O Fe(CO)42- + R Cl (OC)4Fe Fe(CO)5 + RLi O R EtOSO2 F HMPA OEt (OC)4Fe R

E+
(OC)5 Cr

PKa
H CO CR 2 M
CH3

O Me

B- (c)
Nu- (b)

OC CH3

12 25

L (a)
Nuc = RO-, NH3, RNH2 Pequeos R2NH, RSH

Me

O OC O
O

OC
Me O

CO XR

O M= Cr, Mo, W Me X= O, N, O S

11

(d) E+
(OC)5 Cr (OC)5 Cr
(OC)5 Cr

O Me NuO Me hv - calor Bo R CH + R 3

O Me

Me

(OC)5 Cr (OC)4 Cr Nu CH2 R

(OC)5 Cr C O R Me

O Me
CO L

Nu Me Cr

Cr (OC) R 5 Cr (OC) 4 L

MeO O -Me

O Me CH2 R

N
(OC)5 Cr

(OC) Cr O 5 Me
CH3

CH3 BuLi

R = H, Me, Et, CH2Cl

N 1.1 eq O(OC) Cr R O Me 5 O Me OH (OC)5 Cr (OC)5 Cr BF . OEt . 3 2 BF 3 OEt2 R H2C CH2 O

(OC)5 Cr

O Me (OC)5 Cr CH3 ArCHO

Et3N/TMSCl

O Me (OC)5 Cr Ar

OMe (OC) 4Cr L H2 C H

n- BuLi THF -78C

OMe (OC) 4Cr L CH2

R-X THF -78C

OMe (OC) 4Cr L H2 C R MeI = (CO) 22%, (P) 93%

O PhO HO Ph OPh HO 2NaH Ph N O Me Ph N (CO) 5Cr Ph O O

O Me (OC)5 Cr CH3

HN

(CO) 5Cr

N CH

Ph
3

(CO) 5Cr Ph (OC)5 Cr CH3 CH2

N H

(OC) CH2 5 Cr
H

PhO-

O Me CH2 N H

Ph Ph H (CO) 5Cr N CH2 O Ph

Ph

Ph Ph

(CO)5

Cr.Py
(CO) 5Cr

H O O
N CH2 O

Me
(CO) 5Cr

OH

N (OC)

O Me
PhOH CH

Cr 5 O

N
2

CH2

Ph

Ph O O Ph

Ph O N CH2 O Cr(CO) 6

H N (CO) 5Cr CH2

O Et (OC)5 Cr R

Li
-70C a -40C

(OC)5 Cr

O Et R O H X

1) CH3Li o LiBEt3H (OC)5 Cr 2) H2O

O Et R OH H CH3 X

N (OC) 5W Ph

Co2(CO)8 0C 3h

(OC)5W Ph

O C

X (OC)5 Cr R

CeIV O O O

X O R

R= Me, Ph, Bu, X= OEt, OMe, NHPr

OMe (OC) 5Cr Ph

MeO Z

Ph

Z= CO2Me, CONMe2, CN, P(O)(OMe)2, SO2OH

OMe (OC)5 Cr Ph

OMe (OC)4 Cr + Ph CO

X (OC)4 Cr X

OMe Ph

MeO Ph X
eliminacin reductiva

OMe (OC)4Cr H X Ph
b-elim.

OMe (OC)4 Cr Ph H X H
eliminacin reductiva

MeO X

Ph

OMe (OC)5Cr Me OR

80C

OMe Ph

OMe (O 4C)Cr Ph RO

OR (OC)5Cr H

OMe Ph

OMe (OC)5 Cr Bu

THF 100C

Bu OMe

Ph

OMe (OC)5Cr Me

P(O)(OMe)2

P(O)(OMe) 2 MeO Me 75%

Me O Me 16% P(O)(OMe)2

MeO Me 28%

CO 2Me

Me O Me 24% CO2 Me Me

O CO 2Me

O (OC)5Cr Me

NMe4+

1) R2COBr 2) -20C R4 OR3

O R 3O R4 O R1

O (OC)5 Cr NMe4 + COCl 2) -40C Ph

O (OC)5 Cr Me

1)

O Ph

83%

O O 5 C(Cr Ph

O5 C(Cr Ph

O (OC)5Cr Calor Ph

H O 92% H Calor N 61%

Ph

N (OC)5Cr Ph

Ph

(OC)5Cr

OMe H R1 R2

OH R R R2 R2 OMe R R

O C

Cr MeO

OMe (OC)5 Cr (OC)4 Cr

OMe

CO

R C C R

OMe (OC)4 Cr R C C R

C R

OMe R Cr(CO)4

(OC)4Cr

OMe

CO

(OC)4 Cr R

OMe R

H HO OMe R R OMe

R (OC)4 Cr R

MeO MeO

OMe Cr(CO)5

R3SiO BnO OSiR3 Ac2O/Heptano 80C

MeO MeO

OMe

OH OSiR 3

MeO

MeO

OAc OSiR3

1. calor Cr(CO)5 N OMe 2. H+, H2O 3. ox

R2 R1

R1

R2

OMe (OC)5W

HO R 3SiO
1. 120C, 23h

2. ox OMe

R3 ISO

62%

OMe OMe (OC)5 W OSiR3 H (OC)5 W

OMe 2+2 OSiR3 H OMe (OC)4 W

OSiR3

Mettesis

O W OMe CO OSiR 3 W OMe 2+2 W OMe

OSiR 3

OSiR 3

(OC) 4W C

O OMe OSiR3

O MeO

OSiO 3

HO

R3 ISO

62%

OMe (OC)5 Cr calor Cr R1 OMe R2 CO Cr O R1 OMe R2 O R1 R2 Cr OMe

R1

R2

O R1 R2 OMe red R1 R2

O R1 OMe

Cr O

R2

Cr OMe

R1 R2

OMe

X (OC)5 M -CO (OC)4 M

RL

Rs

RL (OC)4 M

Rs X

X=OMe, NR 2

RL O C

RL M(CO) 3 (OC) 4M RS insercin de CO RS X eliminacin reductiva (OC) 4M

RL RS X

O RL RS X

RL RS X

OH RL RS X Derivado fenlico

RL RS X

Derivado indeno

O N (OC)5Cr calor (OC)4 Cr R N Ph R (OC)4Cr R O N R O

R R N O red el H (OC)4 Cr R R N O

R2 HN (OC)5Cr

R1 R1 H H 110C N R2

MeO

OMe

OEt (OC)5Fe Ph

OEt (OC)4Fe Ph

EtO CO (OC)4Fe O

Ph

CO

O (OC)4 Fe O C OEt Ph Fe O C

O C

Ph O

O OEt C Fe Ph

EtO-

O O EtO (OC) 4Fe

Ph O EtO

O Ph O Fe(CO)4 (OC) 3Fe O

OEt Ph

X (OC)4Cr CO R

hv

X (OC)4Cr O R

X (OC)4Cr

R C O

Rxn. Staudinger
N Ph Ph H Ph O C Ph Ph Ph H Ph N O Ph

* N (OC)5Cr H H Cr C O N

N N

O N

* *

Ph N (OC)5 Cr H

O hv

Ph H (OC)4Cr N C O

R3 N

R2 R1

Ph H (OC)4Cr O N

O R3 N R2 1 R CO

H2 N R 3 * * R2 H N R1 O

1. H+ 2. H2 , Pd/C Ph

O N R3 * * R2 N R1

O N N N N

S N

S N OH CO 2Me

OMe Ph

Boc N N

Ph N (OC)5Cr H

O hv CO, CH 2Cl

O N O

Ph O N O OAc HN O

P(O)(OEt)2 CO 2Bn

O N CO 2H OAc

O OAc P(O)(OEt)2 CO 2Bn

OR (OC)5Cr R

hv Et2O, CO

R RO O

Z Cr(CO)6

R = Me, Bu, Ph

R= Me, Et, Bn
Ph OEt

O (OC)5Cr O - NMe 4+ R 1 2 R X OH O (OC)5 Cr n R n

O Cr(CO)6 Me O

n H

Me [(CO)5Cr] O

O n

X R1

R4 R3 X= OR X= NR2

N 2 R O -lactamas

R3 R2 O X R1 X= OR O -lactonas Ar N N Ar O R2 R2 H hv (OC)5 Cr N R
4

hv R4 X R1 R3 R2 hv X R1 O R4 R3 R2 X= OR X= NAr 2

ciclobutanonas hv

Ar X= OMe R1 = Me Ar N N

O OMe Me

O N N Ar

Ar OMe Me N Ar

OMe Me

Diazetidinonas