Vinyllithiums from butyl-vinyl tellurides and bis-vinyl tellurides

Tetrahedron Letters,Vo1.30,No.52,pp Printed in Great Britain

VINYLLITHIUMS

FROM BUTYL-VINYL

Simone M. Barrosa,

0040-4039/89 $3.00 Pergamon Press plc

7353-7356,1989

TELLURIDES

Joso V. Comasseto

AND BIS-VINYL

*b

+ .Oo

TELLURIDES

and Jorge Berriel b

aD epartamento de Quimica Fundamental, Universidade Federal de Pernambuco, Recife (PE) - Brasil b

ABSTRACT:

Duty1 vinyl configuration

Vinylic this

class

tellurides in good

tellurium

species

of organnelemental

communication sources

Instituto de Quimica, IJniversidade de Sdo Paulo, Cx.Postal - 20.780, S&o Paulo (SP) - Brasil

we repor’t

and his-vinyl tellurides furnish vinyllithiurns with yields upon treatment with nbutyllithium at -7X*C.

are

little

compounds the

use

investigated.

Recently

and developed

of butyl

vinyl

several

tellurides

(I) -

and

,TeR’

‘c=c H’

H

This synthetic

1, Table

‘H

(2) - as

efficient

H

\Te’

‘R

2

operation

takes

advantage

of the

softness

of the

tellurium

at -78”C,

atom5.

followed

(2) were

In this

way,

by trapping

isolated

in good

the yields

1)7.

E+, THF

n-BuLi,THF,-78”C,N2

p RCH=CHE

@ [RCH=CHLi]

-1

-78°C

-BuTeR’

R’ =Bu

(1)

-3

,

E+=Cpp+0,

(C6~#0,

In all cases

(analysed

study of 1-Q . In this

preparation

tellurides

‘czc’

1 equivalent of n-butyllithiurn 1 (R' = n-C H ) with 8 9. wrth electrophiles, the vinylic derivatives vinyllithium

treating

intermediate

olefin

his-vinyl

HH

‘CC’ R’

-1

(Eq.

a systematic

for their

of

of vinyllithiums.

R

by

we initiated

methods

retention

(3) and

that

shown

of the

by CC-MS)

of n-butyllithium

CH+CH~+CO,

was

and then

in Table

starting formed trapped

alkyl when with

1 the vinyl an aryl

C~H, 7Br configuration telluride vinyl

(1) was telliide

benzaldehyde.

7353

Scheme

of

the

the

carbon-carbon

same.

(4) - was

A complex

treated

with

I rationalizes

this

double

bond

mixture an equivalent result.

of

the

of products amount

7354

Scheme Path

I n-BuLi T

ArTeCHXH2

1:

CH2=CHLi

_4

Path

2:

n-BuLi _____c

s 8

t ArLi + ArTeBu

-5

_6

+ BuTeCHKH2

_7

_8

-5 + -6 + BuTeBu _9

Path

3:

-4+6-ArTe _

+

2

-5

10 C6H5CH0 Path

4:

)

2, _6

CH2=CHCH(OH)C6H5

+ ArCH(OH)C6H5

-11 p-CH30C6H4

Ar = C6H5;

I n-butyllithium

In path (~),aryllith~um

the

(5),

tellurium

attacks

the

4. Addition ratio.

mixture

the

an alkyl of products.

was easily

configuration sodrum

the

R-CZCH

to

no starting

material

atom

vinyl

of -4 leading to a mixture of vinyllithium (5); in path 2, n-butyllithium attacks

telluride

to 5 or 6 and

to dibutyl

telluride _5 and diary1 reaction mixture (path

to the

in paths

2 and

3 were

telluride

(E),

which

(2); in path can

3, -6 with -5

react

4) leads

to a mixture

confirmed

by using

of -1 I and an excess of

(41, butyl-aryl telluride (7) (10) were _ or diary1 telluride 2, -11 and -12 were detected. The results commented above group must be attached to the tellurium atom of -1 to avoid the formation of a Jn this work we used butyl vinyl tellurides obtaining dibutyl teliuride as by-product,

we

products;

from

Treatment

of

at

-78C”, olefmes

of vinyllithiums

the

only

reaction

developed

an

acetylenes

with

by

(2) in good (Eq.2,

EtOH/H20,N2,reflux

method

tellurides trapping

yields.

to

telluride

In this

prepare

gel.

bis-vinyl

generated

(2) with intermediate

the

on silica

in situ

tellurides

from

elemental

way,

the

2

equivalents vinyllithium

bis-vrnyl

tellurides

of with

n-butyllithium electrophiles

(2) - are

Z

source

in gave of two

1) 2 n-BuLi,THF,-78”C,N2 -2

2) 2 E+,-7X”C,N2

*

2

R\C-C/E “H H’

-3 E+ = C6H5CH0,(C6H5)2C0,

of

tellurium

I).

Table

-

I

(2)

(Eq.2) 438 .

in ethanol-water

bis-vinylrc

followed

by chromatography

disodium

hydroxide the

mixture

efficient

Te/NaBH4/NaOH 2

butyl

1 leading

shown

borohydride/sodium

the corresponding

tellurium

(7) _ and

propositions

reaction

by reactrng

tetrahydrofuran

equivalents

The

separated

Recently

and

attacks

telluride

of benzaldehyde

In this case

among that

which

aryl

of _7 or 5 formed in path tellurium atom of _4 leading

-12 rn a 55/45 n-butyllithium.

show

butyl

atom

regenerating

detected

-12

1

CH2(CH2)4C=0,

CsH, 7Br

(2)

7355

1-

Table

Reaction

of

butyl

n-butyllithium

vinyl

tellurides

followed

(method

by trapping

with

A)

or

bis-vinyl

tellurides

(method

B)

with

electrophiles.

Yield A

(%jb 0

Z-C,H5CH=CHCH(OH)C6H5

sgd

sag

Z-C,H,CH=CHC(C,H,),OH

-

89

Z-C6H5CH=CH&(OH)(CH,),CHZ

79

x2

Z-C6H5CH=CH(CH2),CH3

7oi

7oi

CH2=CHC(C6H

70

-

E-C,H,CH=CHCH(OH)C,H,

79c

-

CH2=C(CI13)CH(OH)C6H5

-

72f

CH,=CHCH(OH)C,H5

x5e

xof

p-BrC6H4CH=CHCH(OH)C6H5

-

66grh

CH3CHXHCH(OH)C6H5

81e

-

p-CH&,H,CH=CHCH(OH)CgHg

-

7og

79o

-

70d

77g

77e

-

7Zd

7Zg

Producta

CH2=C(C,H5)Cti(OH)C6H5

compounds

purified

by

isomer

was

observed

was

both

by reaction

rcflux’;

reagents

chromatography;

trans-b-bromostyrene’,

prepared

under

with

prepared

corresponding

e the

starting

tellurium by

m vlnyhc of the

mixture

of Z/E allylic

alcohols

I-bromooctane

contaminated

with

dissolved

and

telluride

was in THF

detected

was

Grignard

(5 ml) the

prepared bromide.

gthe

reagents;

by 200 MHz reactron

of

with

b

lithium

yield

of the

product

butyltellurolate

NMR

rnixture

borohydride

obtained

by

starting

bis

under

reflux

in ethanol ‘H

sodium

and was

CG-MS; stirred

telluride

Grignard telluride

brominolisis

vinylic

on

of -cis

in ethanol

by reactmn of the vinyl f the starting bis vinylic

(CH2:CRTeBr,

telluride

dat.a;

cis isomer. This percentage d a!cohol; the starting vinylic

telluride

butyl

bromides

spectral

10% of the

in the allylic

with

disodium

mass

substitution

acetylenic

by alkylation

with

and

by vinylic

vinyltellurenyl 3 divinylditellurides ) with acetylenes

I3 C NMR

0

‘prepared

reacting

by reacting

12 h,

NMR,

vinyl

5)2OH

OCH,CH-CHCH(OH)C6H5

tellurides

butyl

R

CH2CH-CHCH(OH)C6H5

corresponding

followed

prepared

the

‘H

satisfactory

column

commercial

was

gave

(%)b

A

-

@aAll

Yield

Product=

of

telluride

the was

’ ; bin this case a 92:8 iafter

at room

the

addition

temperature

of for

7356

As retention

in the

case

of

the

butyl

vinyl

tellurides

the

transmetallation

reaction

occurred

with

of configuration. The

results

tellurides

(2) -

are

synthetic

uses

for

reported

valuable these

Acknowledgements: -

in this

communication

intermediates

compounds

The

authors

CNPq

in

under

acknowledge

the

S.M.B.

for

alkyl

synthesis.

are presently

and CAPES.

(Recife-PE)

show that

organic

investigation

following

of

(1) and bis-vinylic -

of

synthesis

and new

in our laboratory.

for

CAPES

absence.

tellurides

methods

agencies

acknowledges

a leave

vinyl

New

J.B.

for

support:

FAPESP,

a PhD

FINEP, and DQF

fellowship

acknowledges

CNPq

for

a master

fellowship.

References 1.

M.J.

and Notes Dabdoub,

V. Dabdoub,

J.V.

Comasseto

and N.

Petragnani,

3.

Organomet.

Chem.,

308,

21

I

(1986). 2.

M.J.

Dabdoub

and J.V.

Comasseto,

Organometallics,

3.

M.J.

Dabdoub

and J.V.

Comasseto,

J.Organomet.Chem.,

4.

S.M.

Barros,

5.

T.L.

Ho, Tetrahedron,

6.

Two

isolated

Allers,

7.

J.V.

Chem.

Ber.,

Angew.

Typical

procedure:

After

was

(40

removed

benzaldehyde An isolated 15%

yield

reducing The same

allowed

to

agent:

with

brine

two

on --trans-f?-bromc

class

phenyl

V.A. Potapov,

S.V.

I. . <.

Ohe.

in

USA

30

May

1989)

(0.67

ml,

mmol)

aT.

(1989).

Kauffmann

N. Miyoshi,

ml).

The

ethylacetate

(30

organic

and

H.

S. Muray

and N.

at -78°C

under

equivalents

of

with

Ta!zhashi,

M solution

1 mmol)

min),

then

layer

was worked

product.

The

benzaldehyde

added.

with

reaction

and

with

of

performed two

The ethyl

up in the

Elution

was

n-butyllithium

in hexane).

was

was diluted

gel.

usual hexane

bis-vinylic using

equivalents

the of

telluride.

[Z-(CbH5CHXH)2Tel tellurium

A.S.

(4 ml)

1.5

mg,

on silica

the

with

THF

in

1 mmol, (106

chromatography

was obtained H.

(I

by capture

Amosova,

(1987). (Received

(4x15

of bis-vinyllc

of E configuration styrene

8_, 1661

literature:

A. Ogawa,

temperature

of compounds

acetylene

the

bcnzaidehyde

room

with

followed

in

telluride

n-RuLi

by column

above;

of this

compound

Organometallics,

N. Kambc,

vinyl

of

reach

and elution

by reacting

167 (1988).

(1987).

temperature,

were used per equivalent

example

I 187

of the butyl

was purified

described

reported

H”llro,

26,

a solution

n-butyllithium

procedure

z,

and V. Dabdoub,

were bT.

Engl.

this

and washed

residue

with

(1983);

Ed.

at

dibutylrelluride

tellurides same

1001 Int.

dropwise

was

ml),

and the

I&,

stirring

Dabdoub

reaction

To a solution

mixture

acetate way

of

M.J.

84 (1988).

I (1985).

of this

Chem.

added

40 min

reaction

4J,

examples

Sonoda,

nitrogen

8.

Comasseto,

z,

Kashik,

in aqueous Tetrahedron

m 41%

yield

S. Uem.gra,

was

medium Lett.,

by vinylic

N. Sugita,

recently

in the 30,

613

substitution 3.Chem.Soc.

prepared

presence

in

of a

(1989).

of NaZTe Japan,

1469