Tetmhcdron Lcttcrs. Vol. 33. No. 32. pp. 4553-4556.

1992
Printed in Great Britain

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A Novel and Convenient

Approach
bicyclo[3.3.1]nona-3,7-dienes

C. Oliver Kappe,a Gerald Flrber,b

a Institute of Organic

Chemistry,

Curt Wentrup,c and Gert Kollenza*

b Institute of Physical Chemistry,

A-8010

c Department

to Functionalized
2,6,9-Trioxa(Bridged Bis-Dioxines).

Graz,

Karl-Franzens

University Graz,

AUSTRIA.

of Chemistry, The University of Queensland,

Brisbane, Queensland

4072,

AUSTRALIA

Abstract:
The synthesis of N-aryl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamides
2
by reaction of dipivaloylketene-dimer
1 with aromatic amines is described. Bis-derivatives
5, 6 resp.
are formed from 1 and aromatic diamines. The structure of N-phenylcarboxamide
2a was proved by
X-ray
crystallography,
the chirality of these compounds (e.g. 2b) established by NMR studies. A
reasonable reaction pathway for the unusual transformation I -+ 2 is discussed, too.

u-Oxoketenes
under

are

ordinary

protecting

highly

reaction

substituents

dipivaloylketene

and

conditions,

such

as

although

still an a-oxoketene,
currently

Here

we

from

report

reaction
The

was

a new

out

and

ketenes,

in CH2C12

approach

be isolated

can

be

stabilized

have

described

we

sterically

the synthesis

1.1 This highly hindered

to

is not attacked

intriguing

or observed
by

by oxygen

of

ketene,

or moisture1

(11 in our laboratories.

molecule

to 2,6,9-trioxabicyclo[3.3.1]nona-3,7-dienes

amines.

solution

chromatography
(l-24

and

of this

of dipivaloylketene-dimer

by thin layer

Recently,

stable

normally

however,

cyclodimerization

chemistry

efficient

and cannot

groups.

[2+4]

overall

reaction

time

2a-d were

digested

with cold MeCN

the

These

is extremely
the

1 with aromatic

reaction

carried

followed

of

exploring

molecules

reti-butyl

its subsequent

We

are

reactive

1 with

at room

temperature.

which

h; see

p-substituted

revealed

Table

1). After

and thereby

The

a very

amines

progress

of the

pronounced

removal

obtained

aromatic

of the

(1.05

reaction

substituent
solvent,

in good to excellent

equiv.)

the
yield

effect

was
on

products
and high

purity.
Table

reaction
2

2
Scheme

4553

time (h)

mp. (0

24

120-122

bOMe

166-167

NMe2

166-168

NH2

190-192

4554

Structure
indicated
IR

that,

spectra

(1660
the

of these

from

the addition

sharp

showed

cm-11

signals

elucidation
apart

in

assigned

downfield

molecule.

167

tH-NMR

From

these

spectroscopic

taken

place

during

system

2,

spectra
The

The
only

heterocyclic

two

ring

other

system,

metallic

In
bicyclic

in the

= 4.87

step,

the

When

the

aromatic

first

Eu(hfcJ3

amine

(cf.

Michael-type

the final product

2.

best

proposed

present

carbonyl

4.85

was

and

in

4.90

ppm.

must

have

with the

obtained

no

group

rearrangement
reconciled

region

featured

from

bicyclic

an X-ray

(a

1). The

uncommon.

from

There

acetylacetone

selfcondensation

having

a 2-fold

functionalized
was

employed
(200

5.23
for

is rather

are

2,6,9-trioxabicyclo[3,3,l]nona-3,7-diene

(obtained

compounds

was

of 2a.

study

the

unsymmetrical

attacks

addition

between

which

lost. The

via organo-

product

rotational

of triformyl-

axis as the only

axial chirality.4dl5a

spectrum
q

in the

data
been

teti-butylcarbonyf

an unusual
was

had

spectrum

of any

structure

molecules

the

the

CDCls)

of 2

functionality

addition

enol-form

derivatives
by

of

this

1H-NMR

a nice

bridged

studies

splitting (ratio

of e.g. 2b was

using

1:l) of all

observed

(e.g.: S

ppm).

formation

ketene

established

as reagent,

MHz,

and 5.28

it is this nucleophilic
Table

structure

derivative

exhibit

mechanism

likely

that

4,8_dicarbaldehyde

of these

NMR

reaction

donor-substituents

intramolecular

are

proton

Most

in the

both dissymmetric

chirality

of COP

W-NMR

singlet

of data

possessing

1,3,5,7_tetramethyl

ppm; with Eu(hfc13 6

possible

B-ketoamide.
by

The

sharp

molecular

identified

and therefore

2a-d

contrast,

1: The

the

on microanalytical

11.3

reported,

and

are

shift reagents.

A
first

These

signals

(H-8)

the

of symmetry,

system.

chiral
the

namely

intermediates),4

methaneI.5
element

system

compounds

the

absence

evident

of the

of 2a (Figure

Figure

the

ensemble

final confirmation

analysis

based

one equivalent

Moreover,

exhibited

it became

reaction.

initially

1 - only one absorption

to

amide.

demonstrating

data *

that

however,

crystallographic

contrast

ppm,

was

of the amine,

to a carboxylic

from

The

products

is outlined

in a-oxoketene

to the ketene,

of this B-ketoamide

to give trioxabicycle

in Scheme

4. Elimination

now

In the

1 to furnish

that is highly
(3)

2.

undergoes

of CO2 from

accelerated
an

4 leads to

4555

3
Scheme

From

the above,

a similar

way.

2d (cf.

Table

1)

After

known

addition
dioxinone

room

yield.6

when

the
of

only

the

We

with

ring

by

are
or

transformation
to various

amines

equivalent

get

This
research
was
wissenschaftlichen
Forschung

the

further

In addition

functionalized

was

of

the

this

work

of

in the

should

In

(mp.

208-211

hand,

1 with

eventually

due

was
to

the

employed

in this

produced

by

degradation

of the

less nucleophilic

amines

1 under
other

reaction

similar
solution.

metals.4

were

concomitant

in

when

interest,

to transition

other

1 in MeCN

of

dipivaloylacetamides,7

1 and

in

reactions
insights

react

Thus,

corresponding

obtained.

particular

at all with dipivaloylketene-dimer

investigating
to

ketene

or benzylamine)

N-substituted

On

1 the

moiety

diethylamine

of amine.

of

product

are

in general)
diamines.

2 equivalents

precipitated

functionality

nucleophiles
to aromatic

oC)

with

molecules

were

ketene

do not react

2).

270-272

treated

the

(e.g.

products
the

a second

(1 +

(mp.

crab-like

(or

equivalent

ability of the trioxabicyclodiene

to

currently

temperature,
These

isolable

mercaptanes

second

was

amines

this reaction

ether

aliphatic

amine

as p-nitroaniline

alcohols

route

treated

good coordinating

However,

such

at

93%

that other

able to extend

p-phenylendiamine

days
in

reaction,

were

4,4-diamino-diphenyl

two

collected

might expect

we

was

1,4-bis-substituted
experiment

one

So far,

conditions.

nucleophiles,

mechanism
provide

these

such

of this
practical

as

unusual
synthetic

2,6,9-trioxabicyclo[3.3.l]nona-3,7-dienes.
supported
by
the
(grant no. P8318-CHE).

Austrian

Fonds

zur

Forderung

der

4556

REFERENCES

AND NOTES
C. J. Am. Chem. Sot. 1991,113,

1.

Kappe, C. 0.; Evans, R. A.; Kennard,

4234-4237.

2.

AlI new compounds

gave spectroscopic
and analytical data in accordance
with the
assigned structures. Data for compound 2a: IR (KBr): v = 3430 (NH), 3060 (=C-H),
3000-2870
(C-H), 1665,1655sh (C=O), 1600 (C=C) cm-l. 1H-NMR (CDCI,): 8 q 1.04,
1.14, 1.20, 1.24 (4s, 36H, 4 t-butyl), 4.87 (s, lH, q
CH), 7.06-7.53
(m, 5H, Ph) ppm.
IF-NMR
(CD(&),
rrng-carbons
only: 6 = 92.03 (d, lJCH = 164 Hz, C-8), 97.09 and
99.59 (2 m, C-l and C-5), 105.52 (s, C-4), 161.74 and 162.13 (2 m, C-3 and C-7),
166.93 (s, CO) ppm.

3.

X-ray crystallographic
analysis of 2a: A colorless specimen of size 0.84 x 0.30 x 0.30
mm3 was investigated
at ambient temperature.
Crystals are monoclinic, space group
P2,/c, z = 4, L, = 1.08 g/cm3, a q 14.185(21%, b = 11.960(18)A, c = 18,257(3l)A, I3 =
l10.80(10), V = 2895.6 As. Cell parameters were obtained by a least squares fit to the
diffractometer
setting angles of 40 reflections with 20 between 80 and 150. The data
collection for two octants of reciprocal space (MO-K, radiation, x q 0.71069 A, wscans
with variable speed and AO = 1.00) yielded 7414 reflections with 50 < 20 < 55O, 6652
reflections unique, and 2435 with l/o(l) > 2. The structure was solved by direct methods,
after several refinement cycles with isotropic thermal parameters, an empirical absorption
and volume correction
was applied. Finally all non-hydrogen
atoms were refined with
anisotropic thermal parameters, the phenyl group and all methyl groups were treated as
rigid fragments. Torsion angles were refined for the bonds to the pivot atoms. Hydrogenatoms were included in the refinement
with isotropic thermal parameters
(with the
exception of the amide hydrogen). The minimized quantity was z(tF,t - F,I)~, final R =
0.0619 for 373 parameters
and 2435 observations, the final electron difference density
map showed features between -0.16 e-/As and 0.17 e-/As. The atomic co-ordinates
for
this work are available on request from the Director of the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ. Any request should be accompanied
by the full literature citation for this communication.
(a) Gibson, D.; Oldham, C.; Lewis, J.; Lawton, D.; Mason, R.; Robertson, G. B. Nature
(London) 1965, XX?, 580-581. (b) Gibson, D.; Lewis, J.; Oldham, C. J. Chem. Sot. A
1967, 72-77. (c) Mason, R.; Robertson, G. B. J. Chem. Sot. A 1969, 492-497. (d) De
Renzi, A.; Panunzi, A.; PaoIiIIo, L.; Vitagliano, A. J. Organomet. Chem. 1977, 124, 221-226.
(a) Arnold, Z.; Budesinsky, M. ./. Org. Chem., 1988, 53, 5352-5353.
(b) Podlaha, J.;
Podlahova, J.; Arnold, Z.; Maly, K.; Petricek, V. Acta Cryst. 1988,C44, 1966-1968.
IH-NMR spectra of 5 and 6 (200 MHz, CDC13) exhibit only one set of signals in
accordance
with the proposed structures, indicating the presence of one single diastereo-

4.

5.
6.

7.

C. H. L.; Wentrup,

isomer.
e.g.: N-Benzyl-dipivaloylacetamide,
m.p. 130~132 OC; IR (KBr): v = 3340 (NH), 3000-2880
(CH), 1720 (C=O), 1650 (C=O) cm-l; 1H-NMR (CDCl3): S q 1.18 (s, 18H, 2 t-butyl), 4.39
(d, J = 5.5Hz, 2H, CH2), 5.72 (s, lH, CH), 7.12 (br, lH, NH), 7.18-7.35 (m, 5H, Ph) PPm.

(Received in Germany 27 April 1992)