A new method of ring expansion

T.trahedren LottorsNo.18,pp. w%196e, Printedin Groat Britain.

1966. Port”=

Pm*0 Ltd.

AAEWMETBaDCFRINl3~ANSICH Roy

chevron

Wetid,

c.

De 2elms

c!habsl

W.ifamia, U.S.A.

(~oooired5 ?obnwy

Cu~ml or

canpnny

1966)

of eerbooyulio ring synthesis have been the subjeat

methods

(11 Tkb adventof aarbeu~~(~) aousiderabls study. and relsted(3)

aynt.heae~of three-msmberedringshas fwusedreoentattentloninthis

area onthe utll%zatlonoftk3e intervmdic4testoeqandrin.gsbyoneaarbonunits. No%mofthethree~redrlngexpansionmetlMsthus far developedcouldbeoonsideredasbelngof gplurelsynthetla utility (4) dlfflaultylnp-eparatialof due to oompetlngside resotlons,

StArtiq

(6) mEtarlalr,(5) or inherent llmitatlans In theircthemlstry. b nowreport anw~~oithree~eMdringopeningsldone_ ocCbon,ringenlargenlent. Ths procedureemploysndldoondltions, inapredlutabls-1,

proneeds

sndas far as It hasbeen iawsti@tedls not

subjeotto tlm above-ntioned limitations.&he~~Iexempliiiesthe methodwith the exemplesw have studled. ReadIlyavaIlable ketoneswre essilyoonvertedtotheenolesters (I) by the methodof E8gmmyer and EulLt7)

Pretiou reaationsofdiohloro-

(8) Eouever,w carbenewith enolestershsve been ratherdlsaouraging. were able to obtainyieldsor 25 to 50% in the presentlnstsnceswlthout attemptsor optimi%ation.(9) The aoetoxy-ge=diohyalopropsnes, II, ontrea~ntdtha

sll@texaess of lithiumrlumtnumhydrlde in ether at

1965

1966

No.18

(Id (rva)l"

(b2081.1

(b2053')

R / 0ccH3 + NaCCCC13

WCH2CH&M8

P

&Y, 2.5 brs.

-4 oii

/&

n 5 3 (II,b. o7 61'; m, (11)

0.

n

=

bo.03 53') . 4 (II,b3-4 111.;I'JJ boa3 53-5.)

8. n - 5 (II,b2 105';I'J, boBu 63-5")

c\ /c-c1 L?

(IV) (50 to l_

b.

yield)

a. 11I 6 (II,bl 109-X!*; N, bl lC'0.5-l"1")

No.18

1968 intarmbiataIII warrnot Isolateddnae yIeldedmixtures aontainiugonly

II

rduatioa

partial

aperiasnta

andIV. Ituastbsrafazaaonoludsd

that if III had exiated, it must hava raaatedwithl.ithlumalusdnum faster

hydride atamuoh

lha

auth0rwishes

teohiaalaSSiStanoe

rate thaatha eaerespouding II.

to exprefw his gratitudS t0 bfra. 'pbn-llbnL%nfOr and

to

Dr. L

P. Lbdamnof

Cimvrc41ResearahCorpo-

ration for obtal&ngauddlsousslngthsMM2 spetxa.

(1) (2) Reaentlyravlewdin:

byA. T. Rlmqul6t,Aoede111Io Pram, BCW YCar g&

(3)

H.

gg+

g&.,

(RLSwul

KOw

co.1 &

1 (19w.

E. 8lnm~ and R. D. Smith,J. Am. Chem.LOO.,8& 4256 (1959).

ICsren Km& (4) w. IL ~~ham, R. W. &edar, J. R. Tnroalrrmorton, R. 1. D+son, ibid.,8JJ 321 (1565).

and

86 2653 (1964). (5) C. H. De Puy and L. R. Mihcmey,ibid.,Q=., 28 2206 (1963); (6) R, D. De &ha and C. 16 Cabs, J. Crhrg. J. Wol$mby, D. Cjmn,and R. I'Iovak, cham & Ipd.5 (1965). Jr. and D. C. Hull,Jnd. %R. Chem.,& (7) H. J. Hagsmeyer,

2920 (1949).

and 8. Van Der Van, Rec. trav.ohim. (8) W. M. Wa@wr, H. Kloosterziel, 3 740 (1961);C. E, Cook and IL E. Wall,Cham.& Ind.,1927 (1963). (9)

extensiveanddetaIled ~~SOUSS~O~ Of this reaoti~nwlllbe reportedslsewhere.Au alternateapproemhis suggestedin the potentialuse of the trihalamthylmro ma nts developedbyD. 8e@erth St&., J. &II,~hem.SCQ.,8 u%?59 f&G). W compounds reportedhem wma pure by0I.Cand e9 a~~~+ntal. analySeS. Amore

J. Oes. Chem.U.8.8.R.,& 658 (1937). (10)D. v. l5shahenk0, (U

E. Berm,

J. Or& Chem.,3 -

=C

(1963).