Propellanes

Tmahr&mVol. U. No. IS.pi 415 ~04820.19%3 Pmwd I” Grar Brima

PIu)PSLtANXS. XXV.

‘IME

@MB4oiQ/a1) 1300+.00 0 1981 Fwgamon Press pk

pWcILON

TBTiWNlC ?Y)PXLLMXS YiM

01

Chemistry,

18ratl

Institute

~Recekxd

urtrtct

- KMD IB ibtt. to rtplace affordiog the corrtmpondlng

ditntm,

rlogr

Thie reaction

consisttd

dtenophilt qectra

tht forur te(CD)3

More rtccntiy and a aZxturt ether

a mixture

CpCo-dlethtnt

of

the starting

or imidc; of

lsoneric

five

other

in OK t 7 May

complaxt8

of

of various

the

iron

Israel

dtfinition

interacted

In-c(M=?t(Q))3

x) reprtmm

or CpCo), lch

remone

when Pc~(CX))~ ~a@ reacted

could

containing

of

with

utrt

1 but &en

reactive

The ‘H-M(R of the

(tttraanic)

propellane

mixture. 3 Oving to tht hercrocyclic

in principlt,

ring,

one pry obtaln

mono-complexes iaolattd

rcpulrlon

rttrfc

of

a five-rr?abcrcd

2 isomeric

(PTAD).

very

be correlated.

typt

ring*),

products

by this

the configuration

of

in the product

cyclohtxadiene

Indeed floe

noiety

with the smt

1 (---

ttprreent

propellants

trfcerboayl

and products

for

&if*,

with 4-phtnyl-3,5-dloxo-triaxoLlnedtont

the tduct#

oltrrials

prermebly

OF

1988)

md permitted

~8

(2c-e).

in ca 1X yield,

Ttchnoiogy,

were mhouo to be preatnt

lines

products

bls-carplcxen

This occurred

of

wert ltaaurtd groups. 2

of

Interacting

of displaccatnt

CpCo-cmplrxcr

of

cLv oymetry

found

of

and c&t coaftgurattona of

reqtctivt

e.g.

are capable

03NPLtMS

CpcO moieties cooplexed to 1,3Diclr-Alder adduct* of these dienea.

- We have whom that Ft(a)j3

Imtraduttior. cycloheuditna

CRBALT

* loSEill KAPON, AND DAVID GIXSSURG

PNINA ASKKWZL*,

Department of

CYCUMWXADIIWL

4-HETWL-3,S-DIOXO-TRIA2OLINXD’ONE (HTAD)**

2a,b

and 3

when M-Pc(CD),,

between its

Fc(CO)~ was rued,

2c btlog

H groups.4a

only 2c ws

obtained,

in hfgh yitld.4a Dfecumfoa

tn the reaction ooittlem certain

reaponnible

ruing

bia-caplex for

iaolatcd

concentration

(see

** Dcdtcated seminal XIII.

Ginsburg, *Deceamd

not

(frau

of

lurprisfog that no 2c (H=CpcO) could be observtd %?I*steric repulsion of tvo CpCo

CpCo-dierhent.3

the abrtncc

from the ‘IIt-HIIRspectrum

unob8trvablt

Pert

Is is therefore obtafntd

in eht anti,anti

presumably

his

of tlant.mixture

of

of ltaric thir

the reaction

but $eprratlon

of

rtfertoca

potential ofxrurt

is

product.3

the hcttro-ring) Of course,

that 2t is not present

the products

*Iso

showed that

ia

ON MY not be in an

no 2e could

be

belov). fn frleodrhlp

contributions

to tn organocobaltophlle, to tht chemistry

P. Anhkenarf,

J. Mtr. March 9.

ti.

Sot.,

A.L.

Professor

hlbert

of much more complex cobalt

Gutmao, Ash+? Hnndtlbaun,

in prem.

1988.

4815

D. Killer,

Eachennooer,

in honor of

compounds.

U.J.

Richrtr,

end D.

4816

P. A.lHKlwAZI

JN M5kMq qJ

k

li

al.

Cl

M I

-

After

a lecture

lppcrtcd

ho try

In short

order

experience appeared

w

ructica

he inforrd

vith vorthtiile

could

lepemtion

attapt

much reparation

We wre

vae

not

air-stable

looking

PC(a))3

IffAD. Only Zc could mentioned

before,

Two sots rtertind of the

of the

occurr.’

pure

Since DUD.

.o

If n

with

of working

in

both

that

m

rucceeded

bircaplexe#

in working

it

Our 1Cllhof.x

earlier3

cmpoante.

pure wx~~- ad

we bed

propell*ner’

with

work reported

we

with

in

XXAD.

tri~rolinodiaer~

the

to rho need

but

luckily

CpCo-capluer

ln

ltxaphcm

argon

involved

acre

during

rufficiently

unnecessary.

The crude

raction

Although it

the

v~

be lrobted

the

tituree

poaible

cwillg

prepamd

CpCo-caplua both

to ita

in alheir

were

are

lea

#table

to lrolate

tha

end to react

inrtability

then

(#cc uperlxental

the thr

meetion)

with and as

no Xe ue# obtained.

of rxperhents

uterial latter

happily

cmplexcr not

their

of our experience

a procedure

lpainted.

chrm~togr~phic~lly

Joint

diomo,

the pe(C0)3’capluer.

tetmenic

CpCo-cap1ex.a’

the

into

rewtioru

#twer

and Dlrcus~ia.-

correrpondtnp

xixturer

the

fomrd

ruch

w

i&cd

an

to workup.

and irolatia

to uke

Xawltr

easier

for

cajrgetd

uork

of varioru

of their

- 20

of veriau urllcr

raction

dduct#

interectia

to pZAD becwa

derivative

leparetion

atudy

- 2d

at

the dimplacrent

to repeat

2c

CpCo-caplaer

e TAD tollal-

of product

we could

KfAD ve# preferred

the

laagh

kind

-

and birDielr-Alder

to study

MM

M

2b

includi~

uith

UI that

the xcn(r were

the

P. VakLhrdt

their

collaborators

methyl

20

YU dienophile

ruurired

in the

tetmenic

propellene

rare

ratted

carried

vith

uu

prerent

follalng

iride

vith

thrcqthout.

rchaer.

-thy1

at

the pure

1 lq MUD, in the

Dlfferont

In all

the

C~CI

wed,

l.c.

XW

nti

recond

QCo-caplues. with

rrrulta

the wm(r tilde,

In one,

10 eq so thet

yczu obtained

or his-CpCo

the

a lerpc

ucew

and these

caplex

l re

of the

h
+a To

cocp

0

/

\

2a

Xhe referee rtandard

fomulee

hr

luggerted

ured

herein.

that

m

utd

l

full

structural

fomula

to asure

understandillg

of

4817

RopeIIanc5--XCIV

The firet

s&as

shafs

t&s rwults

for

ths corxnrpondig;

raw-syn-caplrr,

2e,

in X

yield.

NMC

NM

MTAO

NMa

MTJID

IO

Scheme

of

stteck ujor

uhen tbsts

th

usked

product

CpCo occurs rsreted

with

is

ring

Although aore

tbrn

syn-uono-Dirla-Alder the

reaction

8rrooXly moiety

period

lntsrventiou

&hue

recovered. little

(uuctmplexsd) frm

nsjor

the

enayrh

ring.

adduct,

the

obssrvsd’)

4 ia

rescttou

ssquencc

But

tire

product

(40X)

is

sas

CpCo is

Sat

likely

this

during

2e (29%) tesctim

an lqulvalsnt

1s *sin

of

rsuaed

sepsrstiou

thsn Fe(CO)2

simply

product

out,

of

ir

the nsksd of wwwwwwwwwW

sdduct

5 for

1s the cobslt-free sfthsr

CpCo is

st

vis

iepottmt,instsnce

air

tks very

cmplsxed

no such “rpoatmsas cvidsntly

the

loss

of Fad

by a huge excess

rue,

of products. (ubsrs

falls uors

in either

is

I.8 wed,

Yhcn excess

syn-sttsck

3 1m surrounded

still

MY

step

of MUD

of this

but in 8-s 5% yield.

24X of the product

systsn

Aoother,

utsrfel

thsn the sya,ryPbis-DieirAlder

sod it

neceassry.

40

the first

cams

(66%)

sddwt

> 66%).

4.

AOOUCTS

stsrtiag

Whoa

such l o ettsck

HEAD rvsiiable,

or POR

of clcLv ir

fa

5

5

Dut in botb

cyclohsxsdieos

prsclssly

step

(probably

4

24

tine lyn-

nection

of MUD.

to the sywsono-Dfels-Alder

to the propsllsdfens us8 lsrllsr

dlscwaed

other

no excssa

2s the first

cyclohexadieot

thars

is

3 nsults lcsdiu~

rolecules.

for the ssns

1 clhmm that

bs isolated

NMt

66 31

29

I.1

)IMlt

of actallic

losr

oxidstion.

of slailsr

end of

Icrs

No

behavior

in

klsu.

2 shmts thst

the snti-rcucrCpCo-capllplu,

The major product 6 results

two products

further

l rs

rsaction

yeia

4 (LLX)

of 4 uith

fra

attick

snd 3 (5X)

HUD,

Zb, of the

rssultiag

respectivsly.

uith

I.1

es HfM,

psnits

neked eyclahcrrdiene fro

loss

rink

33% to br whilst

of sme CpCo frcr

the

6 and

P. A.snmA2.l

4818

MTAD

NYg

al.

Cl

A

N

CPCO

N +

2b

- 2b

-6

33 -

50

-4 MTAD

I. I

IO

However in

when

18X,

.n

26X,

(10 eq)

ucee. end 5U%,

Scheme 3 ehow

the

NM8

of ~AII

ie

the

the

vith

no Zb ir

med.

vhere

khevior

4,

end 5 l re

of the

lyn,enti-bircaplu

2d.

NW

N+ N*N -2d

product* i.e.

behevior ir

and 6,

NMI

I.1

76

IO

44

l re

obteined

2d ie

lyn-CpCo group ie rlnoved there

recovered

MTAD

greetert,

the

56

2

of the

lpperently

the

in

I2 I

pony

in preference

no ruch

to

in type the

lyo,eoti-Fe(CO)3 relectivity.lb

II

I

22

32

3

lech cue,

ltebleet

enelogour

2.

+

Scheme

ie

5

II

rerpectively.

-2d

e-e

5

26

CPCO A CPQ

Ihe

Y?

N

AWUCTS

18

Schema

forred

NM8

NMc

NMt

the

reletive

2 pruducte.

lnti

one (Cf.

cmplex

lhoun.

eaounte There

2d ->

of the

ie

cleer 6).

tetreenic

tlcro

recovery

iadicetion

Thie

ie

not

propellane

thet

in

line

imide

4819

PropellriXs--xctv Albeit

we know the lu-lMR spsctrum

the crude survive

ructioo

mixture

the sopsration

unsyretrlc&l

oaly

procedure.

bie-cupIex

id

is

the syn,ryn-bis-CpCo-co.Plex3

of

Zb, and 2d were isolated.

2a,

Again a syn-CpCo misty rtabie

under

the lme

upon chrautography

‘f’hc fourth

is

rather

treatmax

usily

duriq

of

component 2c does not renovcd

but the and

8ep8ration

isolitlon. When 2d is created aa w-pared

vitb

cobalt-lesr

uterial

of

f 4:l.

with cerlc

uooiun

1, th

syn CpCo group

here ll80,

l’hu8,

it

f8 tsrfer

mixture,

Dr. G. Yilke

Prof.

alxtures

tetra8nic

of

preparstions. additional

for

propellane

rt8y

st flulheim/Ruhr

plate

P. vollbrdt

of

the crude

hfs

isolated.

private

comunications

us enough crude

reaction

and to Herr L. Stchliug

hospitality of

by a factor

nor othervise

for

for

with CpCo-dlethene

In the sumer

to conP1stely

to the snti-group

in the NHR 8pectrtm

to prepare

owes royal

CpCo is not ss selective

the sp-moiety.

to Professor

fifde8

of

in addition

on the chromtogrsphic

his kfod a~reaent

Again ooe of us (D.G.)

resow1

18 removed em corpsred

2e w8e obaervrd

nor va8 any observed

AtZkSnI~ed#meut8.-We are grateful

lSKIto

(3 cq)

Nevcrtholesr,

to ceaovc

None of the lnti,anti-C&O-complex reaction

nitrate

lna10g.~

the syn,anti-bfs-Pc(OD)3

to Professor

Yilkr

these

for

during

sn

1986.

w spectrs were measured in RtOIc on a 5rsy IS spcctraeter. IR spectrs 4MhSMAt.were messured in 0W3 using a Perkio Llrer 298 spectrometer. Wit spectra were measured in CDC13 on a Bruker 400 KHz spectrometer. Msss spectra were Plcnaured on s Varian XAT ill spectrometer. All mp’s (from EtOAc) are uncorrected. sepmr8tIon.was separated with EtOAc (3):

hcune

were isolated. unstable of

a) The crude

resction

on dry columns of (7)

On the

elueat.

JJ

the

crude mixture

JIPC

Hcune

conditions

sdded to evsporated if

pure products

mother

were very airilar

2s:

h.p.

1385,

(dd.

2H.

3.74

(dd,

74.94,

8-e

2b: 1382,

(s, 2d:

ZH, ss=e J’s, J2,3-2.3. 80.37, (6).

252 (88).

247-248’C. 1380,

272 (6)s

461.0235,

fdd,

1010.

Co-vinyllc), 76.03,

4.69 2.88

15.82,

252 (53).

found 46L.0221.

found

(s,

‘Li-NM: (8,

121.68,

(dd,

5 Cp H),

3 NC3&,, 2.82

58.65,

189 (1001,

56.53, 187 (9).

in 8oLutfon amounts

and the three

of

On the other

hJRd,

l).

IR: 1780,

J2,3-2.6,

vinylie),

(log

252 (42).

264 (4.163.

the

1708, 5.57

5 Cp H),

(8,

118.43,

187 (63,

80.19,

2.95

76.42,

80.21,

128 (47),

(dd,

ZH, sue

128 (71,

fdd,

ZH, J-2,2

56.28,

1435,

2H, 8aae J’s, Co-vinylie),

55.37,

24.56.

no fluorercence.

IR:

J2,3-2.4,Co-vfnylic),

; Cp H),

24.28.

5.64 cd,

1708,

U8: 337,

found 337.0543.

268 (4.40); (s,

1770,

IR:

vlnylic~,

Cp H),

28, J 3 494.4,

53.98,

w

272 (5.4),

337.0512.

4.58

products.

337.0534.

332 (3.46). 5.32

stood

J2 3-2.4, Co-viaylic), 4.72 1J C-NhR (100 HRs): 126.59,

(s,*5

MU: &lc.

trfturation

(11 mg) was

procedures.

J2 3=2.1,

4.83

ia Clearly

decomposition

ZH, J3,4-7.5,

334 (3.2),

2H, J3 4’7.8,

128 (34).

8) and 1 (25 ~8s)

b) Rspid

The relative

266 (4.25),

335 (32).

125.68,

a ppt of

2a.

(dd,

f8.‘3NQII).

Co-vinylicf:

8)

plates

S102.

2H, J3 4’4.3,

UV: 388 (3.13).

1295,

into

338 (3.3).

337.0513,

SiO2).

(2.1

silics

gave a ppt of 2d (17 ~1.

gave

separation

or over

UV: 388 (2.863,

vith

2c but vhen this

in both

3.09

l3 C- NhR (100 KHz):

Co-vlnylic), 79.38,

(dec).

2H, J-2.02,

335 (46), h.p.

(dd,

and 2a (0.33

(16 mg) end b part

decomposed

U8: 337. U+(78,,

lH-NtlR: 5.94

(d,

‘JNC,).

1435,

4.83

C18H,6ND2Co: Cslc.

1010.

solid

’ H-NhR (400 MHz): 5.72

Co-vlnylicf,

24.89.

226-23O’C

5.05

H+(lOO,, 1700,

W:

1290,

vinylic),

J’8,

39.45,

Ln the dark,

388 sh (2.98).

vinylic),

SH, 8-e

!&p.

W:

g),

and/or

with benzene

in solution

1018 cm-‘.

J’s,

60.89,

124 (100).

2.74

200-202°C. 1295,

2b (0.23

and CpCo-diethene

by preparative

the lH-NhR Spectrum of 2c3 it

to contain

this

folloved

solution

give

appeJred

isomer Zd, remained unchsnged 1440,

liquor

SiO2 us8 then used,

isolated

(in

and treatment

This fraction

particularly

g)* of

(48 ~8) with EtOk,

of mother liquor

hexane-soluble.

of the methylinlde 100-200)

2d (1.23

of our knowledge

ba~i8

under the separstion

Cwporstion

oixturr (Uoeln

rilic~

3.07

fdd,

ZH, J3 4-4.4, 1J c-NUR: 178.43, Co-vinylic).

J’s,

I(s: 461,

124 (52).

1768,

4.80

(dd,

h+(88),

W:

376 (91,

337 (71,

C23H2lH02Co2: Cslc-

310

4820 Iuctiou and 10 tq.

flltercd, htunc

tie& re~p~~fvely)

Schue

n.p.

3: 6.01

(t.,

2H,

f&N).

&lc.

270-274’C

(38

4.68

(I,

mg) geve

UV:

It),

5 Cp I).

3.20

80.16,

76.51,

13C: 128.14,

252 (13).

450.0738,

found 450.0765.

producta

(2.64).

(dd, (e,

189 (41),

Schme

the productr

whovn in Scheme 2.

6: n.p.

’ 28O’C.

406 (2.63).

(s,

5 cp H), 75.42,

189 (13).

2.92

57.36,

identical

24.83.

with

with

leparetion

1pecioen8.

ceric

salt

6 (21 mg) with ceric

lalt

(58 mg),

5X)

1790,

1720.

4.78

W:

J-3-4,

2.86

US: 450,

124 (66).

+i-IMR

(t,

(es

&1.4),

337

$1R19N4D4@:

when 10 lq WTADlre wed.

(st

MS: 450,

reectione

II:

1785,

1725.

4.95

3N(II3).

n+(l6),

(G

‘R-NHR: 6.64

J=3.4.

2%

13C: 175.88,

337 (28).

(t.

E-N),

127.85,

285 (81,

252 (13)~

of td with different 6 was identical

plete

2e (18 q,

ueing

13.5X),

uounte

thet

ceric

of

deecribed

uuronium nitrate

EtOAc(4):

hexene(i)

end 2b (80 op,

HeOH(i) (10 ml) wing

to an authentic l

to

mAD*

2d

lbove,

4

L

(68 mg) in EtOAc(3):

gave 4 (18 mg; 92%) identicel

4 (2 rp;

Co-vioylic),

25.11.

128 (S),

2.75

IP:

J’e,

C+vioYlfC),

- 2d (200 mg) with

on a prep Si02

1 (23 mg, 27X),

66X),

speciaen8.1

of the

OP.

u;

EcOAc (7):’

luple8.’

124 (56).

to authentic the results

producte

daretaleted

3 (27 q) aa eluent

25.47,

usIn

Co-VioYlfc),

25.50,

270 (4.08).

J2,3-2.3,

128 (30),

to luthentfc

fdcnticel

g8ve in HeOH after completely

161 (100).

to MALI (gee mounts recovered).

1~ the =oet et&le

of

49.39,

(33

(4.09).

2?i, e-e

49.06.

(m, 3Ni2$ + ZH, Co-vinYLic),

3 emrixeo

hutment

(dd,

328 (2.941,

2H,J3,1’4.2.

161 (loo),

4 and 5 vere

and 5 were

(dd,

54.79,

165 (66),

Schuc

W: 5.09

3.04

262

J2,3’2.2,

1 shovll the producte

Zb gave

If),

(2.88).

55.10,

165 (34).

eq

lpec1sene.l

332

3Nq13).

3,

W~AKI(1.1

The whole war

to eutheatfc

Za (11 mg; 29X),

211, J3,4-4.2,

55.41(q),

48h.

with

on prep SiO2 pletes

were ideorical

luthentic

to

to arand for

effected

recovered

388

4.97

or 2d ue~ each treeted

end rlloved

Co-less

identlcel

(dec).

2 vln~lic

2 vinylie

81.91,

end 2e

Za, Ib,

leperetlon

and

caeea

285 (69),

J-3.4, k.71

in lll

4 end 5 were

J-3.4,

3NCIff). (13),

eq)

1).

procedure:

ECOAc rolution

in

ee riuent.

HTAD (1.1

- General

lveporeted

the solvent (3)

(see

tffm.

u

(474 mg, 3 eq) cluent

gave

59.5X). XtOAc(7):

hexsnc(3)

specimen.’

e lbove gave identical

4 (IS mg; 98X).

PEFKRBNCeS 1. 2.

l) kI.

Korat, 0. Tatereky, and D. Cinrburg, htrebedror, 26, 2313 (1972). b) C. Amith and D. Cinrburg, ibid., 30, 3415 (1974). C. Anith, and 0. Clneburg, Bclr. (Mm. &t.a, K. Bachmen, U. van Phfliprborn, (1977).

3.

4.

5.

60,

400

42, 2559 (1986). 0. Ginsburg, L. StchlIog, C. Wilke, R. Berm. and R. Goddard, htrahdnm, N. Reshcf, A& D. Ginsburg, TeLrabdrOQ, a) J. Altman, E. Cohen, f. Haymon, J.B. Petcraen, htrrMrcm bf K.B. Birnbaur, J. Altman, T. Uaynon, end D. Clneburp, 25, 5115 (1969). cf. c) K.B. Birnbaum. kti -St., 281, 161 (1972) md d) G.1. IlttcrB, 2051 (1970). Birnbaua, J. k. 5~. Sot., 94, 2458 (1972). K.P.C. Vollhardt, prlvete coprunicetion.