Free radical type addition of toluenesulfonyl cyanide to unsaturated hydrocarbons

Tetrahedron Letters,Vo1.28,No.25,pp Printed in Great Britain

FREE RADICAL

TYPE ADDITION

OF TOLUENESULFONYL

TO UNSATURATED Jim-Min Department

Fang*

of Chemistry, Taipei,

0040-4039/87 $3.00 + .OO Pergamon Journals Ltd.

2853-2856,1987

Taiwan,

CYANIDE

HYDROCARBONS and Ming-Yi

Chen

National

Taiwan

University

Republic

of China

Summary: By catalysis of AIBN, tosyl cyanide adds in a regio- and stereoselective manner to unsaturated hydrocarbons, including alkenes, dienes and 1-hexyne. Accompanied intramolecular cyclization and ring cleavage were 1,5-cyclooctadiene and pinenes. effected in reactions with norbornadiene, Toluenesulfonyl

cyanide

(TsCN)

has been successfully

Due to the strong

induction

utilized

of the sulfonyl

in many

group,

TsCN

synthetic

aspects.

functions

as a CN transfer agent in reactions with C-, N-, 0- and S1 The reaction is thought to involve an addition-elimination

nucleophiles.

TsCN a12so undergoes

process. dipolar

species.

sulfonyl

group.

especially

cycloadditions

The reactivity

investigated

is greatly

The cycloaddition

us3eful intermediate

nucleosides.

However, except

readily

product

enhanced

for a preliminary

1,3-dienes

by the effect

and 1,3of the

from TsCN and cyclopentadiene

in preparation

the free radical

with

of the carbocyclic

type reaction

report

analogs

is an of

of TsCN was rarely

of the photochemical

reaction

of

TsCN with three alkenes, including an ambiguous stereochemical outcome in one 4 example. We thus further exploited the free radical type addition of TsCN to a variety Under appropriate benzene

of unsaturated an atmosphere unsaturated

hydrocarbons. of nitrogen, hydrocarbon

(or 1,2-dichlorobenzene,

Exclusion

of oxygen

analysis,

and the products

shown

in Table

fashion. account

were

I, the reaction

of TsCN

The reaction

isolated

with AIBN

was monitored

in a regio-

t

Me2C(CN1* Ts* Ts++

t

_N

TsCN

--3

P

2

scheme

2 Me2C(CN)* Ts*

t

)c=c:

+

Ts-+

t

--*

Ts+-+-CN

TsCN

2853

(0.25 mmol). by the TLC method.

As

and stereoselective

in the following

for this result. Me2C(CNlN=NC(CN)Me2

and an

in refluxing

by the chromatographic

proceeded

as depicted

(2.5 mmoll

was performed

25 mL) by initiation

was necessary.

A chain mechanism

the reaction (25 mmol)

Me2C(CNj2

+

Ts*

is proposed

to

2854

Table I, _

Real

3

4

5

Yield, %

18

80

20

70

80

6

[3$ X4% YmH: 72 @4$ X-H, Y=CN:6 c&d: 5

120

16

78

4

?I

0

6% 0 8;

I sotuted

80

I

2

ion

TlhR;e

*

6

ci9-

120

36

15

7

49 ~

120

36

16

60

24

68

60

24

80

36

8 9 0

X

(@I):

58

(9&

30

QQ.g): 31 (l0&:

29

2855

Entry Similar

2 indicated

this reaction

stereochemistry

was further

and 1,5-cyclooctadiene to norbornadiene

to give exe

thus provided

an intramolecular

diene,

On the other

(416

the strained Similar

Although

previous Thus,

conditions.

(%)

regioselective nearly

addition

and

addition

the cyano

functional

groups

the organic

synthesis

Corson,

Gratitude

A. M.; Jagt,

lx,

gave a single

product

also produced

unsuccessful

was realized

($1 in a the

attempt,4

by catalysis

isomers

(21

and

(3)

in

for preparation

Since

furthur

the chemistry

application

Shie-Ming

Peng

of compounds of these

of our method

Science

Council

(the National

in

for

Taiwan

J. C. Tetrahedron

J. Th. Tetrahedron Cm.

ll,

u.

lm,

w.

lz,

36, 1654.

967.

(b)

3763.

(cl

(dl Treuner,

U.

559. R. G.; Nyquist,

(bl Van Leusen,

Jagt,

J. C.; Van Leusen,

3. (al Cermak,

A. M. &.

R. G.; Evans,

J. C. Tetrahedron E.

R. Tetrahedron

N. J. ?I. Org.

Y. J. J. m.

Research

M. la

S. J.; Davies,

C&.

&.

and w Chem.

D. J. 2. Org.

J. K.; Singer,

35,

la,

(c)

92, 1343.

1974, 39,564.

Lett.ym,

(Ml,768

lz,

1970, 971.

des m-Bas

22, 2331.

1981, 46, 3268.

T. E. J. !&LII. a.

S. J.; Harrington,

F. P. J. w.

Chim. -A. M. 4. Org. Cm.

R. C.; Vince,

5. (a) Cristol,

E. B.; Corson,

A. M.; Jagt,

J. C.; Van Leusen,

B. L.; Oppenheimer,

Cristol,

cycloaddi-

and Notes:

4096.

4. Pews,

undergoes

for X-ray measurements.

2. (a) Pews,

Cherng,

(&I.

in the free radical

is due to the National

F. P.; Pews, R. G. 4. Org.

(d) Jagt,

that TsCN

method

groups.

developed, a is promising.

M. S. A.; Hackmann,

Synthesis,

(5-1 in a 71 % yield.

to previous

an expedient

and to Professor

1. (a) Van Leusen, Vrijland,

compound

an opening7of

of product

resulted

two geometric

of TsCN

1,5-cycloocta-

caused

2,3-dimethyl-1,3-butadiene

are well

support,

University)

compound

to cyclopentadiene

and sulfonyl

Acknowledgment. financial

norbornadiene

addition

With

(%I.'

a low yield

1,4-additions

with

with

to give the bicylic

has demonstrated

afforded

we provide

containing

References

to produce

of anti addition.

amounts.

summary,

In

product

of TsCN to 1-hexyne

but the reaction

equal

in reactions

of TsCN to 6-pinene

On contrary

(2).

in the manner Homoconjugative

occurred

afforded

report

The reaction

yield.

1,4-adducts of AIBN,

ring

a-pinene

1,3-dienes, 2 we found

tion with modest

the major

addition

hand,

with

revealed adducts.

cyclization

four-membered

reaction

occurred

m.

(c) Fang,

(b) Kam, J. M.;

(S), 180.

Commun.

w,

1397.

1964, 29, 1282.

M. S. J. cm.

&.

(b) lm, 88,

1529. 6. (al Dowbenko,

R. Tetrahedron

1964, 20, 1843.

(b) Dowbenko,

R. J. Am.

2856

m.

(c) Friedman,

l/$&l, 86, 946.

&.

(d) Winkler,

J. D.; Sridar,

L. 3. &I. m.

G .; Alvernhe,

G.; Laurent,

V. J. -Am. Chem. a. A. Tetrahedron u.

7. Oldroyd,

D. M.; Fisher,

G. S.; Goldblatt,

w,

&.

1964, 86,

108, 17Or

1885.

(e) Haufe,

1986, 27, 4449. L. G.

Am. Chem. ---

Sot.

1950,

72, 2407. 8. (a) Rappoport, Pub.

(b) Jones,

Oxford, 9.

(IR, (G),

1979, Vol. 3, pp 171-213.

All products

MS,

(4), (a)

'C (lit."

H-7),

1.85-2.07 s), 2.47 3.04

in CDC13)

1.75-1.78

(1 H, s, H-4), 3.01

crystalline (lit."

(i), mp 117-118'C;

of (3a) and (3) were

2.44

(1 H, m, H-l),

(2 H, m, H-5, H-6),

confirmed

are reported

(3 H, s), 2.51 7.36-7.75

in 6 values:

(4 H, m);

q

(Z), mp 136-138 (a),

(%),

mp 109-110 mp 96-97'C.

diffractions (a),

'H NMR

1.68

(1 H, t, J =

1.86 (1 H, cl, J = 1.2 Hz,

(1 H, s, H-3),

(1 H, ddd, J

7.34-7.74

123-124'C;

spectra

(z), (s),

Some of pertinent

(1 H, ddd, J = 15.4, 2.89

Products

compounds.

by X-ray

on request).

and compatible

211-212OC);

(G),

(2 H, m, H-l, H-2),

(1 H, s, H-5),

(5 H, m), 2.18

analyses

structures.

mp 212-214'C

data are available

(obtained

5.1 Hz, H-6),

elemental

are colorless

(a),

107-1lO'C);

(supplemental

HZ,

and (a)

133-135'C);

The structures spectra

had satisfactory

l3C NMR) for the proposed

'H and

OC (lit.4

2.39

z. Ed. The Chemistry -of the Cyan0 Group, x, Interscience D. N. Ed. In Comprehensive Organic Chemisry, PergaItIOn:

2.55

H-7),

(1 H, d, J = 12

(it,, 1.24-1.34

(2 H, m),

12.0, 5.5 Hz, H-3),

2.43

15.4, 12.5, 7.4 Hz, H-2),

(4 H, m);

(3 H, 2.98-

(z), 1.28 (3 H, s), 1.30 (3 H,

s), 1.66 (1 H, m), 2.44 (3 H, s), 3.66 (2 H, s, H-7), 5.45 (1 l-l,br s, H-2), 7.36-7.75 (4 H, m); (&), 2.41 (1 H, ddd, J = 14.7, 4.5, 4.2 HZ, H-4 ), 2.43 (3 H, s), 2.82

4.2,

2.7,

(1 H, ddd, J = 14.7, 8.4,

2.7 Hz, H-3),

4.32

dd, J = 5.6, 2.7 Hz, H-2), (4 H, m); 3.82

(2 H, s), 7.33-7.70

(3 H, s), 3.03 s), 2.79 2.63

J.

C.

q

(1 H, dd, J

(4 H, m);

(2 H, s), 3.80

(2 H, t), 6.82

(2 H, t), 6.23

lo. Jagt,

6.04

1.40 (1 H, s), 1.84

(B),

2.7 Hz, H-4 ), 3.60

(1 H, ddd, J

5.6, 2.1 Hz, H-l),

(2 H, s), 7.33-7.76 7.32-7.76

Ph. D. Thesis,

Groningen

78.

(Received in Japan 31 January 19871

H-5),

5.87

(1 H,

7.33-7.72

(3 H, s), 3.03

(2 H, s),

1.73 (1 H, s), 1.85 (1 H, s), 2.44

(1 H, s), 7.36-7.76

(1 H, $1,

q

(1 H, s), 2.42 (s),

(1 H, ddd, J =

6.4, 4.5, 2.1 Hz,

(4 H, m);

(4 H, m).

(s),

(E), 2.41

2.45

(3 H,

(3 H, s),

(4 H, m). University,

The Netherlands,

E,