Catalytic oxidation and fine chemicals

Catalysis Today,1(1987)351-355 Elsevier Science Publishers B.V., Amsterdam -

CATALYTIC

R.A.

OXIDATION

AND

There

B.V..

is an

P.O.

manufacture.

cleaner,

more

constraints, familiar

sort

thermal to the

liquid

Since chemo-,

the

Consequently, its

rather

the

absence

readily

These transfer

and

with

OXYGEN

are

concerned

oxygen

(ref.

such

may

producers

contain

of

be

these

for

who

the

are

limited

largely

confined

constraints

althoughh

as H202,

other

be ruled

either

low

activity

functional

groups,

a

t-Bu08H

out

as an oxidant functional

range (TBHP)

appear

peroxide

to

of

co-products

because

groups,

and

of

even

relatively

in

cheap,

NaOCl.

which

in

broad

scope

in

have

is particularly

the

considerations.

important

various

catalysts,

hand,

various

also

however,

attractive of

oxidations

since with

recycled.

- GENERAL are

SCHEME

collectively

described

by the

b ATALYST

X-O-Y

Within

will

be employed,

towards

are,

Hydrogen

On the

which

Because

conditions

are

often

of metal

be readily

+

can

There

1).

TRANSFER

envisage?

often

reactivity

conveniently

s

chemical

fine

need

environmental

increasing

to

bulk

in

the

effects:

latter.

oxidants

reactions,

methods

catalytic

of two

temperatures.

strereoselectivity

is water. can

of

due of

do we

catalysts

a variety

synthesis

use

molecules,

moderate

of a catalyst.

available

or R,NO

organic

the

molecular

coproduct

CATALYTIC

and

indiscriminate

combination organic

oxidations

molecules

regio-

the

Netherlands.

processes.

of most

with

The

a result

integration

heterogeneous

be a problem

towards

technologies

catalytic

phase

or

AB Venlo.

is largely

forward

catalytic of

stability

homogeneous

TBHP

the

5900

trend

This

efficient

and

with

What

Box 81.

increasing

chemicals

the

CHEMICALS

SHELDON

Oce-Andeno

may

FINE

351

Printed in The Netherlands

us0

S = Substrate

X;-0-Y-R-0-OH,Na-O-Cl.

1

referred general

+

to

equation

as

catalytic

oxygen

1.

(1)

XY

SO = Oxidized

substrate

RN-O,

3

etc.

The

active

complex,

oxidant

R02M)

may

be a metal-oxygen

or a high-valent

M

oxometal

OS.

row

favour

e.g.

MO,

oxometal

involve

either

elements

such

oxometal

and

CATALYTIC The

elements,

formation Ti,

tend

species, as Se,

known of

(ref.

catalyzed

Fe,

and

second

row

the

and

early

shown:

oxygen

elements,

transition

species.

substrate.

catalyze

VIII

and Group

peroxometal

on

also

oxygen

with

hydroperoxides.

the

and

(80-12O'C)

mechanism widely

(ref.

Some

elements,

metals,

Several

transfer

Ru and

e.g.

V.

non-transition

reactions,

via

both

the

compounds,

c

and

The

reaction (reaction WV1

,

3

heterogeneous

Shell,

metal

oxide VI e.g. MO

of propylene

CATALYST R0g-I ----+CHpI--CH2

+

(Ti Iv/

respectively.

transfer in the

evidence

cycloperoxymetallation

ilq

is

catalyzed is 2)

used and

VVand

,

is

Ti*'.

oxidants.

in hydrocarbon

discussed

/R

transfer

SiO,)

These

solvents

and

(2)

catalysts

systems have

ROH

operate

been

widely

are

used

at moderate applied

in

3).

of oxygen

convincing

metal

active

+

(MO")

by ARC0

synthesis

alkyl production

high-valent are

homogeneous

temperatures

pseudo

Mn

involve

As

2) for the

species

industrially,

been

as

oxometal

of catalytic

CH3CH-CH2

has

a peroxometal

pathways.

olefins

by certain

Peroxometal

presented

Cr,

depending

example

industrially

The

M = P, formed

-O

whilst to

Sn and

peroxometal

epoxidation

organic

(e.g.

EPOXIDATION

best

Both

species,

complex

<“l;;+02R

R02H

transition

W, Zr and

donor

peroxometal

n++

l, First

=

from

literature

from

peroxometal (ref.

competitive

mechanism

+

the

shown

4).

complex

Recently,

kinetic

to

the

Mimoun

studies

/R

+(

Lo M\

G=T

M\O

P

fast)

[/OR +

0

%%

(ref.

favouring

below:

rate

olefin 5) the

353 Until

quite

anhydrous (ref. a

recently,

the

conditions

6),

however,

wide

water

soluble

10% aqueous

variety

of

tungstate-phosphate

H202 can

arsenate)

primary

olefins.

under

olefins (or

H202 as the

use of

or

be used

mild

oxidant

According for

the

conditions

catalyst

under

was to

a

confined recent

selective

to report

epoxidation

using

a

phase-transfer

of

two-component conditions.

ALCOHOL OXIDATIONS One of

the

most

the

common reactions

alcohols

to

corresponding

reagents

has been described,

economically

attractive

combinations

are

For

example,

primary

there

in

secondary using

phosphomolybdate

organic

is

synthesis

compounds. still

both

is

Although

a need

the a

oxidation

wide

metal

of

variety

of

are

both

-

R02H

for reagents which and

and chemo-/regioselective,

promising

OH groups

in

carbonyl

catalyst

respects.

alcohols

are

(ref. 8) catalyst

oxidized

selectively

TBHP in combination

a

with

VO

in the

(ACAC)~

or H202 with an ammonium

presence (ref.

molybdate

7)

of or

catalyst

(ref. 9): t-Bu02H (Y HO

(3)

VO (acac) c

OH

OH

0 96%

>

H20+$03

c

(NH4 )6M0,0~~/

(4)

BuqNClj TBHP in selective

the

presence

oxidation

of

of

a Zr

primary

IV

catalyst,

alcohols

on the to

the

other

hand,

corresponding

catalyzes aldehydes

the (ref.

10):

RWoH

t-Bu02H (5) ZrO (acac) 2

The use of different dramatic

differences

oxygen donors with the same catalyst in

chemoselectivity

as

can

shown

also (ref.

lead

to 11):

354 These reagents example,

can also be used for the oxidative

the W042-/P043-

1.2-dials

system described

to dicarboxylic

water-insoluble Another selective

acids

(ref. 12).

This

diols under phase transfer

interesting oxidation

development

of olefins.

cleavage

above catalyzes system

of 1,2-diols.

of

was

to

also

applied

conditions.

is the use of Ti'"-zeolite

alcohols

For

the H202 oxidation

catalysts

and diols under mild

for

conditions

the (ref.

13).

ASY~ETRIC

OXIDATION

The synthetic considerably

of

metal

by the use of chiral

most well-known alcohols

utility

example

developed

is

the

catalyst-peroxide

ligands to catalytic

by Sharpless

efect

asymmetric

asymmetric

and coworkers

reagents

was

oxidation.

epoxidation

of

interesting

proteins I:1

as chiral

complex

between

enantioselective affording

recent development ligands

catalyst

1,2-diofs

The development prochiral

BIOMETRIC

(VI)

for the

oxidation

and

bovin

oxidation

of catalytic

reagents

will continue

systems

of

(&A)

olefins

the

is with

for the enantioselective

an TBHP,

oxidation

of

context

of

(ref. 17) in the design

of

to be an important

which

mono-oxygenases.

processes

goal

with Fe, Mn

activity mimic

can

the

The latter catalyze

and are thought

as the active oxidant.

in combination

in

the

to involve a high-valent

Initial studies mainly

and

ubiquitous

Cr

porphyrin

cytochrome

a wide variety of

employed

catalysts.

in

oxoiron iodosyl

Mn

vivo

porphyrin benzene

generally

being

to Fe in these in vitro systems.

However,

both components

iodosylbenzene

is

unstable

to oxidizing

the epoxidation

cocatalyst Another

have

expensive

catalyze

porphyrin

albumin

available

example,

synthesis.

catalytic

superior

For

OXIDATION

P450-containing

species

serum

hydroxylation

cis

In recent years, there has been profilic model

catalysts.

in up to 68% e.e.

substrates

fine chemicals

osmium

78% 97%

(ref. 16) is the use of readily

in asymmetric

The

allylic

(refs. 14, 15) e.g.

Yield e.e.

Another

extended

disadvantages

and

conditions.

porphyrin

from

ligands

catalyst

developments

by the more

synthetic both

More recently Mn porphyrins

of olefins

is robust

the

replacement

metal

of

and

imidazole

conditions of

viewpoint:

expensive

have been shown to

with H202 in the presence

(ref. 18) or with NaCl under phase transfer promising

a are

the

as

(ref. 19). delicate

heteropolytungstates

of

metal general

355 formula,

(Bu4N)4HMPW1,039

iodosylbenzene.

These

homogeneous

catalysts

interesting

to see

(where

catalysts with

how

they

the

=

M

Mnrl to

appear stability

function

or

ColI)

combine

the

of heterogeneous

with

cheap

oxygen

in

combination

high ones

donors

with

reactivity and

such

it would H202

as

of be and

NaOCl.

CONCLUDING

REMARKS

We may

conclude

is a fluorishing in the

industrial

from area

the

above

of research

synthesis

discussion which

of fine

may

that

selective

be expected

to

catalytic find

wide

oxidation application

chemicals.

REFERENCES R.A. Sheldon, Bull. Sot. Chim. Belg., 94 (1985) 651. R. Landau, G.A. Sullivan and D. Brown, Chem. Tech.. (1979) 602. in "Aspects of Homogeneous Catalysis", Vol. 4 (R. Ugo, Ed.), 3 R.A. Sheldon D. Reidel. Dordrecht, 1981, p.1. Pure Appl. Chem., 4 For a recent review see F. di Furia and G. Modena, 54, (1982) 1853. See lecture of H. Mimoun, Catal. Today. 1 (1987) xxx. E. Alneri and M. Ricci, J. org. Chem., 48 (1983) 3831. 65 C. Venturello, K. Jitsukawa and S. Teranishi. Tetrahedron Lett., 7 K. Kaneda, Y. Kawanishi.

:

24 (1983) 5009. T. Yoshida. H. Nishihara. Y. Ishii and M. Ogawa, 8 K. Yamawaki, Commun., 16 (1986) 537. B.M. Trost and Y. Masuyama, Tetrehedron lett., 25 (1984) 173. and S. Teranishi, Chem. Lett., (1984) 1: K. Kaneda. Y. Kawanishi

Synth.

1481.

in "Activation of Dioxygen Species and 11 K. Kaneda and S. Teranishi. Homogeneous Catalytic Oxidation", Abstracts of the International Symposium held in Galzignano, Italy, June 24-29, 1984. and M. Ricci. J. Org. Chem., 51 (1986) 1599; for a related 12 C. Venture110 glycol cleavage with VO(acac)2/TBHP see M. Zviely, A. Goldman, I. Kirson and E. Glotter, J. Chem. Sot. Perkin Trans, I, (1986) 299. A. Esposito and F. Buonomo, Pat. Appl., 100 (1984) 119; 13 C. Neri. B. Anfossi, C. Neri and F. Buonomo, Eur. Pat. Appl. 102 (1984) 97; A. Esposito, C. Neri and F. Buonomo, Eur. Pat. Appl. 102 (1984) 655, all to Anic. 14 J.G. Hill, K.B. Sharpless, C.M. Exon and R. Regenye, Org. Synth.. 63 (1984) xxx. see: M.G. Finn and K.B. Sharpless. in "Asymmetric 15 For recent reviews Synthesis", Vol. 5, (J.D. Morrison, Ed.), Academic Press. New York, 1985, p. 247; B.E. Rossiter, ibid, p. 194; B.E. Rossiter in "Catalysis of Organic Reactions", (R.L. Augustine, Ed.), Dekker, New York, 1985. p. 295. T. Uchida, S. Tanimoto and M. Okano, J. Chem. Sot. 16 T. Kokubo, T. Sugimoto. Chem. Commun.. (19831 769. see: C.L. Hill and R.B. Brown, J. Chem. Sot., 17 For leading references 108 (1986) 536. Renaud, P. Battioni, J.F. Bartok and D. Mansuy. J. Chem. Sot., Chem. 18 J.P. Commun.. (1985) 888. Collman. I.J. Brauman, B. Meunier. T. Hayashi. T. Kodadek and 19 J.P. S.A. Raybuck. J. Amer. Chem. Sot.. 107 (1985) 2000 and references cited therein.