1,5-methano[10]annulene (bicyclo[5.3.1]undeca-1,3,5,7,9-pentaene)

Tetrahedron Letters No.

37,

pp

3239 - 3240, 1977. Pergmon PITS-. Printed in Great Britain.

I ,5-METHANO[

IOIANNULENE

(BICYCLO[5.3.1]UNDECA-1,3,5,7,9+ENTAENE)

Satoru Department

Masamune* of

Edmonton, (Received Further we wish

to

to

our

record

hydrocarbon

(I_),

of

Reduction

lowed

of

the

hydroxy of

yielded

the

spectrum

signals

these

of

due

fold

to ring

I ,6-methano

counterpart,

an observation to

7 signals

curren;

is the

reminiscent

evaluate

in

at

depth

4, I

2G2

on

was

azodicarboxylate

4 and

in

the

induced

in

this

5 by

of

low

silica

upon

alcohol

region

monocyclic

structure

leads

1 extends naphthalene of

1 when

at

and

to

the

and

into azulene

an X-ray

In the (see

analysis

high

The

H

that

contrast visible Fig. has

2. 4. 8.

XY = 0 X = OBz, Y = H X = 02CNHC6H4N02

3239

3. 6.

X = H, Y = OH X = OH, Y = H

5. 7.

in CMR

therefore field

a

to

its

region, I). been

pleted.’

I.

NMR

I

give

I .3

interpretation

system. deeply

to

molecule

the

the

isocyanate

300°C

the of

fol-

and

crystalline

Appearance

IOa-electron

of

between

(-80’~)

scale.

equiv-

stereochemistry

formation

trophenyl

orange,

two

led

overnight.’

The

elimination

provided

parent -70°C

chromatography

of

p-ni

at with

O’C

7.

manner

6 with

temperature

aromatic

treated

column

system,

crystalline

hydride

6 and the

ring

the

at

gel

pyrolytic

NMR time

of

subsequently

alcohols,

6 rests

absorption

comparison

electronic

at

1,5-methano[lO]annulene properties

3 which

underwent

the

the

diethyl

5, and _ Treatment

those

the

Alberta

diisobutylaluminum

corresponding

even

least

the

with

chromatography

electronic

of

2l

and

8 which

only

b and

ketone

the

3, _ Table).

(deactivated)

C(ll)-Ha

of

physical

benzoates

gel

symmetry,

T6G

important

compound

of

urethane

ica

Brooks of

Canada

construction

acid,

afforded

(see

1 exhibits

known

isomeric

compounds

Alberta,

and

benzoic

groups

Sil

the

endo-hydroxy

corresponding

two

the

benzoxy

diamagnetic

intend

the

hydrolysis or

20% yield.

possesses

of

resulting

by alkaline

the

spectra

ea.

to

on

synthesis

triphenylphosphrne,

Separation

of

report

first

Dee W.

University

1977; received in UK for publication 2.5July 1977)

USA 6 June

recent

the

stereospecifically alents

in

and

Chemistry,

X = OBz, Y = H X = OH, Y = H

We com-

324@

Table 1.

_

3.

CMR (acetone-d ) : 6 34.7 (t), b 125.13 133.51 (d), 14 g .5V (d), 161 .I6 (s). PMR : 6 2.05 (br d, J=l2.0 Hz, I, H-II), Hz, I, H-I'), 6.00 (m, 5), 6.44 2.0

(d, c-8), 4

_*

5. 6. W

7.

Spectral

1.

Properties (d),

of

128.70

2.38

(d,

(s,

3.40

1,

C-4

or

OH),

-9),

3.10

130.41

(ddd,

(d,

J=12.0

or -4),

C-9 Hz,

J=4.0

Hz,

5.26

(dd,

PMR : 6 2.26 (br dd, J=12.0 Hz, J=4.0 Hz, I, H-II), 3.16 (sa c-')* (d, J=lO.O Hz, 1, H-IO), 7.47 (m, 3), 8.07 (m. 2).

(m,

2),

5.52

(m,

2),

5.96

(m,

5),

6.70

PMR : 6 2.40 (dd, ~~12.0 HZ, J=4.0 Hz, 1, H-II), 3.00 (d, J=l2.0 Hz, I, H-ll), 3.45 (m, 1, H-7), 6.00 (m, a), 7.45 (m, 3), 8.06 (m, 2). PMR : 6 2.14 (m, 2), 3.08 (m, 2), 4.10 (d, J=4.0 Hz, 1, H-8), 5.48 (dd, J=lO.O Hz, J=4.o Hz, 1, H-9), 5.92 (m, 5), 6.55 (d, J=lO.O Hz, 1, H-lo); CMR : 6 26.4 (t, C-II), 46.1 (d, C-7), 72.4 (d, c-8), 123.1 (d), 124.0 (d), 126.6 (d), 128.3 (d), '29.4 (d), '32.3 (d), '34-o (d), 141.1 (5, C-l). PMR : 6 2.34 (m, 2), 2.88 (br d, J=12.0 Hz, 1, H-11), 3.37 (m, 1, H-7). 4.44 (dd, J=2.5 Hz, J=l.5 Hz, 1, H-IO), 5.90 (m, 7); CMR : 6 26.4 (t, C-l'), 43.7 (d, C-7), 71.2 (d, c-lo), '22.2 (d), 123.3 (d), 127.0 (d), 127.8 (d), 131.9 (d), '35.4 (d), '35.7 (d), '46.6 (S, c-1).

a NMR spectra pounds

gave

use parent

Me4Si ions

as of

reference satisfactory

and

COCl3 as solvent, unless otherwise accurate mass (MS-50). b Multiplicity

specified. in

Al' corn--œ

off-resonance

spectra.

7.45 5

4

w

$ -w 3

A PMR [(CO3)CO]

spectrum

500

400

300

of

1

600

W-d Fig.

Uv spectra

1.

(cyclohexane)

naphthalene

(-

-),

K.

Morio,

of and

1 (-),

S. The of

Masamune,

0.

W.

presence

of

1 in

technical

procedure 2.

A.

K.

3.

Because

4.

We thank

a crude

problems was

Bose, of

Brooks,

mixture in

(---).

and

and

R.

was

assured

isolation

L.

Notes

Sobczak,

J.

Am. --

previously

we were

Chem.

+.,

(GLC-mass),

unable

to

obtain

98, but

8277

because

mainly

1 until

the

(1976).

present

developed.

B.

Lal,

thermal

the

involved

1,6-methano[lO]annulene(----),

azulene

References 1.

J=

J-10.0 Hz, J=2.o HZ, 1, H-9), 6 31.2 (dd, C-l'), 42.2 (d, C-7), 72.3 (d), 129.4 (d), 131.0 (d), 131.6 (d), '41.2

(m, 1, H-7), 4.65 (m, 1, H-8), (br d, J=lO.O Hz, I, H-IO); CMR :

122.5 (d), 126.8 (d), 127.2 (d), 128.6

Compoundsa

National

W. A.

Hoffman

instability Research

of

111,

and

M.

1 no attempt

Council

of

S.

Manhas,

was

Canada

for

made

Tetrahedron to

financial

measure

Letters, its

support.

melting

1619 Point.

(1973).