Allylic amination of alkenes by tosyliminoiodobenzene: manganese porphyrins as suitable catalysts

Tetrahedron Printed in

Letters,Vol.29,No.l6,pp Great Britain

oo40-4039/88 $3.00 Pergarnon Press plc

1927-1930,1988

ALLYLIC AUINATIO~ OF MXERES

+

-00

BY TOSYLIHIHOIOJXXU3NZENE :

MANGANESE PORPEYRIUS AS SUITABLE CATALYSTS

J.P. WHY, Laboratoire Universite

G. BEDI, P. BA'JXIONI,and D. MNSUY*

de Chimie et Biochimie Pharmacologiques et Toxicologiques, UA 400 CNRS, Rene Descartes, 45 rue des Saints-Peres, 75270 Paris Cddex 06. France.

Abstract : Manganese-porphyrins and particularly Mn(TPP)(C104) were found to be much better catalysts than iron-porphyrins for allylic N-tosylamination of alkenes by tosyliminoiodobenzene. With the former catalysts, cyclohexene was selectively transformed into 3-tosylaminocyclohexene with yields up to 70% and cis- and trans-hex-2-ene into allylic N-tosylamines with yields around 40X, whereas cyclooctene led to the corresponding allylic and homoallylic N-tosylamines.

Iron- and manganese-tetraphenylporphyrins of tosyliminoiodobenzene, respectively) alkenes

alkylethylenes

catalyzed

a different In a typical

5M in anhydrous

iodobensene

experiment,

is almost

with alkenes,

a solution

quantitatively

(T8NH2)

and the N-tosylasiridines

samples

(3), and four allylic analysis

(C,H,N,S),

within

N-tosylamines,

lhmCPP)(ClO~)

Phi

+

N-tosylamination

as eluent).

with authentic from

'H NNR data (7) (eq.1).

"+A+

Tst4E2+ 4

2.

1

1 compares

the yields

formed upon reaction of various

were

p.Toluenesulfonamide

by comparison

+AOQTs+Lc UETS

NETS

presence

to the catalyst)

(2,3). As shown by gas chromatography

+ PhI=lrrs

Table

of alkenes.

(5) 2.5mM and cis-hex-2-ene

'y"+&

(3+4+5+6) ----

of

of 1,2-di-

(3). This paper

3, 4, 2 and 5, were identified and

(3 and 8%

less than 30 min. The other products

identified

spectrometry

moiety

of a manganese-porphyrin,

(6) (20 eq. relative

on Si02 (CH2C12

1 and 1 were

mass

stereospecific

of Mn(TCDPP)(C1041

sieves

low yields

the N-tosylaziridination

leads to allylic

of molecular

chromatography

with

of the N-tosyl

for the N-tosylaziridination

in the presence

and mainly

in the presence

was formed almost

(eq.1)

In particular,

by Fe(TDCPP(4))(C104) of PhIaNTs

chemoselectivity

by thin-layer

elemental

(2,3).

catalysts

CH2C12 was added to solid PhI=NTs

under argon at 2O*C,

separated

are efficient

with good yields

shows that the reaction

the insertion

into a C-H bond of cyclohexane

cl).. Iron-porphyrins

by PhI=NTs

exhibits

PhI=NTs,

catalyze

of,N-tosylaziridines

of cis-, and trans-hex-2-ene

Fe- or Mn-porphyrin

catalysts. 1927

a

5

4

(1 + 2) and allylic with PhI=NTs

N-tosylamines

in the

1928

Table

1 : Allylic

amination

a nd trans-hex-2-ene

versus

catalyzed

N-tosylaziridination

by Fe-

in reactions

of

PhI=NTs with

cis-

and Mn-porphyrins. I

Yields (!G)' as a functionof the catalystnature Alkene

Products Fe(TPK4))(C104) Fe(TDCPP)(C104) Mn(TPP)(C104) Mn(TDCPP)(C104)

is-hex-Z-ene

N-tosylaziridines (AZ)

12

35

c2

11

Allylic

20

13

37

26

tosylamines

(AA)

R = AA/AZ

cans-hex-2-ene

1.7

0.4

N-tosylaziridines

27

33

Allylic

30

23

tosylamines

R L AA/AZ

1.1

>I8

2.4

t2

4

41

0.7

35

> 20

0.7

a) Yields of ’PS NH, t N-tosylaziridines and allylic N-tosylamines, based on starting PhI=NTs,were detertined by gas chromatography using N-cyclohexyl-p-toluenesulfonamide internal standard. In all PhI=NTs or transfer total

cases,

of

of

NTs to

yields

the

total

an intermediate

of

the

alkene

NTs transfer (Table

varied

very

the

cement

of

Fe by Mn led

particular, its with

almost

cis

in

the

to

those

2 shows

presence used

of

addition

to

complete

transformation

3 equiv.

insertion

as

-10. of the

be much less presence

of

Fe-

similar

with

4 were

formed

allylic

obtained

to

in

the of

Surprisingly,

the into their

or Mn porphyrins

either

N-tosylamines

alkenes

were

close

to

(between

two porphyrin

for

into

derived

100%. The

32 and 57% or

allylic

allylic

6 to

37

ratio(R)

ligands

of

of

from

: N-tosylaziridines

by a factor

catalyst

also

for

the

reactions

used,

20.

repla-

In

N-tosylamination.

N-tosylamines

the

reaction

reaction

of

75% in S.

third

product

a homoallylic cis-isomers (81,

In

in 40% yield

or along formed

its with

convert

case

along

with

above,

isomers of

to

the

reaction

derived

from are

from PhImO in

known to

the

NTs transfer N-tosylamines

5 and fr. These

was

allylic

trans-alk-2-enes

PhI=NTs with

its

almost the

expected

allylic

with

since

its

cyclooctene

amount of

Two major

cis-isomer.

led

PhI=NTs

was completely

cyclohexene

transfer

the

with

identical

was obtained

was formally

Whereas

oxygen

two minor

of

lJ,

C-H bond. towards

upon reaction

cyclohexene

Mn(TDCPP)(C104)

formed,

alkenes

conditions

A 70% yield

to

In the

as mentioned

several

under of

S.

was used

presence

of

catalysts

-9 was obtained

trans-hex-2-ene

from both

the

ratio

converted

catalysts,

This

PhI=NTs

than

For

3-tosylaminocyclohexene

and a yield

NTs moiety

or Mn-porphyrins

this

from hydrolysis

products were

N-tosylamines

or Mn(TDCPP)(C104)

the N-tosylaziridine

reactive

in

the

N-tosylaziridines.

catalyst.

of

Fe-

catalyst.

were

With both only

as the

selective

the

and of

N-tosylamines)

to be the best

results

Mn(TPP)(C104)

and led

Mn(TDCPP)(C104)

N-tosylamine

of

previously.

chemoselective

less

appeared

the

with allylic

increase

came presumably

(2,3),

+ allylic

the

and trans-hex-2-ene

no formation

Table

of

a large

Mn(TPP)(C104)

presence,

TsNH2, which

complex

similar

11, but

nature

to

of

(aziridines were

and 43% respectively) much with

yields metal=NTs

as an

was -3 and

two latter

hex-1-ene.

However,

in

1929

the particular allylic this

case

of

this

N-tosylamination case

Table

even

Fe(TPP)(C104)

N-tosylaziridines

of

with

alkene,

(3)than various

N-tosylaziridination

Mn-porphyrins

and Fe(TDCPP)(C104)

ratios

2 : Reactions

terminal

their alkenes

led

to

manganese with

was more

as catalysts. lower

It

allylic

is

important

noteworthy

N-tosylamines

that

than even

in

:

analogues.

PhIaNTs

catalyzed

Yields

by Mn-porphyrins.

(Xl(‘) as s function catalyst nature

of the

Products

Alkene

Hn(TPP)(C104)

/ S-tosylaminocyclohexene

Cyclohexene

8(b)

Cyclooctyl-N-tosylsziridine Cyclooctene

MnmcPP)K104)

40

70

$o’

9

11

S-tosylaminocyclooctene

X(b)

17

15

4-tosylaminocyclooctene

jJlb)

16

13

I

Cis-hex-2-ene

17

10

14

9

a

Cl

I+2

(2

4

c4

5

22

17

4

16

11

2

2

7

Cl

6

-Zl

20

23

1.

6

4

6

3

4

2-butyl-N-tosylaziridineIcb) Hex-l -ene

3

5

2

Tram-hex-2-em

11(c)

c2

I+2 1 4

(a) Based on starting PhI=NTs, determined by gas chromatography using N-cyclohexyl-p-toluenesulfonamide as in internal standard. (b) N-tosylatiridines 7 and 9 (31, and 3-tosylaminocyclohexene (9) were identified by comparison with autEentic_samples. The structure of N-tosylamines zand J_l was established from elemental analysis (C,H,N,S) and 1~ NHR and mass spectroscopy (7). (c) Only the cis isomer was formed.

The most PhI=O, hydrogen free

the

mechanism

analogue

atom abstraction

radical

similar

oxygen

likely

like

mechanism

reactivity (scheme

of

for

PhI=NTs,

from

the

in

hydroxylation

the

hydrocarbon

(MI1 0’) 1) with

alkane

(8,101.

hydrogen

presence

and alkene of

Our results atom abstraction

Sche

Fe-

by a high-valent

I

could

allylic

hydroxylation

or Mn-porphyrins, metal-oxo be explained

by a high-valent

by

involves

complex

having

by a Mn-nitrene

a

1930

intermediate (i)

the

from

A;

nature

of

a transfer

and B’ in

(ii) the

IV * a Mn - NTs species

(formally

of

the case

the

four

allylic

the NHTs ligand

preferential of

of

Mn”

formation

hex-2-enes

(3)).

Such a mechanism

N-tosylamines

(iii)

of

the

obtained

to

the mesomeric

3 and 5,

formation

from of

would

take

from hex-2-enes forms

of

into

which

the

the more stable

allylic secondary

11 from cyclooctene

via

account would

derive

radicals

A’

radical

an homoallylic

radical. The present

work confirms

alkenes

varies

greatly

various

iron-porphyrins

N-tosylaziridination catalyst

for

to allylic

origin

of

this

are possible

of

the

access

with

insertion

the

intermediates

the of

chemoselectivity the

catalyst.

studied,Fe(TDCPP)(C104)

was the shows

of

(3).

This

paper

the NTs moiety since

chemoselectivity in these

into

PhI=NTs of

reactions

is

of It

alkenes

N-tosylamines, different

that nature

best

that

allylic prepared

high-valent remains

NTs transfer

was previously catalyst

for

Mn(TPPj(C104) C-H bonds from Phi

Fe-

from PhI=NTs shown that stereospecific is

the

best

and provides

an easy

in

(6).

two steps

and Mn-nitrene

to

among the

complexes

The which

to be determined.

References Breslow, R ; Gellman, S.H., J. Chem. Sot., Chem. Commun., 1982, 1400. Mansuy, D. ; Mahy, J.P. ; Dureault, A. ; Bedi, G. ; Battioni, P., J. Chem. Sot., Chem. 2. Cormnun. 1984, 1161. Mahy, J.P. ; Bedi, G. ; Battioni, P. ; Mansuy, D., J. Chem. Sot., Perkin Trans II, in 3. press. TDCPP and TPP stand respectively for the dianions of meso-tetra-orthodichlorophenyl4. porphyrin and meso-tetraphenylporphyrin. The perchlorato-Mn(III)-porphyrins were prepared as follows : a solution of 5.1(r6moI of 5. Mn(TPP)(Cl) (3.5mg) or Mn(TDCPP)(Cl) (4.8 mg) in 1 ml of anhydrous Cl$C12is added under The mixture is stirred until the argon to 5.2 mg of solid AgC104 (2.5 lG- mol). perchlorato-Mn(III)-porphyrin is formed as shown by WV-visible spectroscopy (Amax = 390, 474, 525, 570, 605 nm for Mn(TPP)(ClOq)and Amax = 382, 472, 580, 690 mn for Mn(TDCPP)(CI04)). The solution is then filtered to eliminate the excess of solid AgC104. Yamamada, Y. ; Yamamoto, T. ; Okawara, M., Chem. Lett. 1975, 361. 6. Mass (E.I.) and 1H NMR (CDC13, 2O”C, a:ppm/MqSi)) characteristics of the allylic 7. N-tosylamines. J=7.5Hs) ; 1-1.5(m,2H) ; 2 : m/z=91(100%) ; 155(50%) ; 224(82%) ; 253(1X) ;8=0.82(t,3H, 1.92(d,3H,J=7.5Hz) ; 2.40(s,3H) ; 3.58(m,lH) ; 4.35(d,lH,Jz9.5Hs) ; 5.04(m,lH) ; ; 7.72(d,2H,J=7.5Hz) ; 5.35(m,lH) ; 7.28(d,2H,J=7.5Hs) m/s=91(100%) ; 155(25X) ; 238(22%) ; 253(1X) ;8=0.82(t,3H, J=7.5Hz) ; 1-1.5(m,2H) ; 4: 1.92(dt,2H) ; 2.40(s,3H) ; 3.86(m,lH) ; 4.31(d,lH,JP9.5Hzl ; 5.13(m,lH) ; 5.42(m,lH) ; 7.28(d,2H,J=7.5Hz) ; 7.70(d,2H,J=7.5Hz). 5 : m/s=91(100%) ; 98(44X) ; 155(33%) ; 184(10X) : 210(8%) ; 224 (10%) ; 253(3X) ; -6=0.82(t,3H,J=7.5Hz) ;l-l.O8(m,2H) ; 1.92(dt, 2H) ; 2.40(s,3H) ; 3.5(dd,lH) ; 4.24(t,lH,J=lOHz) ; 5.00(dd,lH) ; 5.30(dt,lH) ; 7d31(d,2H,J17.5Hz) ; 7.72(d,2H,Jg7.5Hz). Because of its low yields, fi was only identified by G.C-mass spectrometry (m/z=91 ; 210(75%) 253(1X)) and by 1~ NMR spectroscopy (signal due to the proton (100%) ; 155(68X) ina to the NHTs group at 3.95 ppm (m,lH)). 3, 3 and 2 were found as trans-isomers as shown by a 15Hz value for the coupling constant between the vinylic protons. : mlz=91(100%) ; 124(17%) ; 155(40X) ; 210(26%) ; 279(8%) ; 6=1-2(m,8H) ; 2!40(dt,2H) ; 2.42(s,3H) ; 4.18(m,lH) ; 4.34(d,lH,J*9.6Hs) ; 5.l(m,lH) ; 5.58(m,lH) ; 7.26(d,2H,J=7.5Hz) ; 7.74(d,2H,J=7.5Hs). : m/z~91(100%1 ; 124(35X) ; 155(23X) ; 184(25X) ; 210(15%) ; 236(21%) .; 279(25X) ; ; 3.44(m,lH) ; 4.35(d,lH,J=lOHs) ; 5.48(m,lH) ; &;“;$H ; 2.08(dd,2H) ; 2.4l(s,3H) ; 7.29(d,2H,J=7.5Hz) ; 7.75(d,2H,J=7.5Hs). m, a. a) Groves, J.T. ; Kruper, W.J. ; Nemo, T.E. ; Myers, R.S., J. Mol. Catal., 1980, 1, 169. b) Lindsay-Smith, J.R. ; Sleath, P.R., J. Chem. Sot., Perkin Trans II 1982, 1009. a) Sharpless, K.B. ; Hori,T. ; Truesdale, L.K. ; Dietrich, C.O. J. Am. Chem. Sot. 1976, 9. 98, 279, b) Sharpless, K.B. ; Mori, T. J. Org. Chem. 1976, 41, 176. M. ; Mansuy, D., Tetrahedron 10. a Fontecave, 1984, 40, 4294, s Groves, J.T. ; Subramanian, D.V., J. Am. Chem. Sot. 1984, 106, 2177. 1.

(.Received

in

France

19

January

1988)