Temhednm Letters. Vo1.31. No.31. pp43894390.1990 Ri in Great Britain

oo4o-4039/90 $3.00 + .oo Per&mm Press plc

A CONWNU3NT GAS CHROMATOORAPHIC MRI’HOD FOR THB

OPTICAL PURlTY DEl-ERh4MATION OF CHIRAL EFQXY ALCOHOLS

William Dougherty, Frank liotta, Donna Mondimore and Wilfred Shum’ ARC0 Chemical Company, Newtown Square. PA. 19073, U.S.A.

Homochinlepoxyalcohols,Which~be ammiently pqmred fmm pfochhnl allylic alcohols by the Sharpless catalytic asymaw%ic epoxidation. have found wide applications in organic synthesis. As an example, glycidol, the simplest of these epoxy alcohols. haa been used for the prepa+m of (p-blockers’. lipids’. epichlorohydM, and L+(+amitine’. Par optical purity de&mmtionofthcseepoxyalalhols,themostcommon methodisthepmpamtionofthe diestereomeric Moaherester8with a-mewxy-a4fhlo~yl~ylxceticacid. Recently, gas chromatogmphic sepamtion of tMuommetylated derhm&s of epoxy ak44mls was mporteds using glass capillary cohmns coated with peralkylated a-cyclw as stakmry pha8e. We report here

. sepalationofthl!desynthetiallyusefldepoxyakoholsonrammemuy mmilable‘fuseddica capillary gc column coated with a mom pok pemethylated hydroxypropyl derimtk of afcydodextrin. rti8lIommhythatourmethoddoexnotlequhederi~foraomeofthe more volatile, short-chain epoxy alcohols.

Resuleofepoxy~l~~a30mx0.25mm~~~pameChylQ hydroxypropyl orcydodextrin A-PHcohmmare - a.linTabk 1. -Il~~ampomdswere prepared by mymmehic epoxidation ofallylic akohols’ and were dmmeked speumcopically beforeuse. Trifl llomwtymwascaliedoutindichlommethrne 8ohmtatMomtaqKmme

Iamine.

a

Table 1. Gas~DataonEpoayAkobolSepUation

EEY

I

2

3

4

5

6

7

8

Teatv:C seprrrCioaFu%or- Qmpomd Ebttionofder

0

P ~Cl$OH 60 1.03 R.S

i&&F, 45 NotRCXtkd

0 .,P3

0 ‘tCH@ 65 1.08 S,R

l.OS S.R

(Figure I). Since~oompowdsuewunsoluble,UleiropClalplrltydetamiortionbmwt easily accomplkbed by direct analysis on the queous extrqt of the epoxidatkn mixture. For the less volatile epoxy alcohols such as 3-ptopylgJycidol, detiv&&on is necmsary for atantiotneric

separation (entry 8). For glycidol 1, the R-isomer elutes before the S-isomer, whereas for methyJglycidols 2 and

2, it is the S -isomerthatelutes6rst. Tlte2-methylgJycidolandits&rivat%aisohaveopposite

elution order (2 and 9’. but the 3-methylglycidol and its deriwtive have simk ehttion otder (2 and

6). 1tisthereforedifEculttodeduce m01ecularconfigumtionofthweepoxyalcoholsbasedonthei.r

elution order.

1. 2. 3.

4. 5.

6.

7.

8.

J. M. Khmder, S. Y. Ko and K. B. Sharpless. 1. Chg. Ghan., 51.3710 (1986). C. E. Burgos, D. E. Ayer and R. A. Johnson, 1: Cl J. J. Baldwin, A. W. Raab, K. Men&r, B. H. P 4876 (1978).

. ug. Chan., a.4973 (1987). Lnson and D. E. McClure. J. Org. Ghan., 43,

W. Shum, manuscript in prepamtion. W. A. Konig. S. Iutz, CL Wenz, G. Gorgen, C. Neumann, Chem. Jnt. Ed. Engl.. 28, 178 (1989).

A. Gabler and W. Boland, Angew.

Advanced !kpamtion Technologies Inc., New Jersey, U.S.A. This type of derivatized cyclodextrin column was developed by D. W. Armsbong: D. W. Armstrong, W. Ii and J. F’itha, Anal. Chem.. 62,214 (1990). Y. Gao. R. M. Hanson. J. M. Klunder. S. Y. Ko. H. Masamune and K. B. Sharoless. J. Am. &an. Sot,. 109.5765 (1987): Chind e& alcohols 1.2. and 2 are n&v available &iiii%iCO --m~lla~. USA.

(Received in USA 17 April 1990)