Tcnahcdron Lc~ms. Vol. 34. No. 32, pp. 5095-5096. 1993

Printed in Circa~ Britain

oo40-4039193 S6.00 + .clo Pergamm Press Lul

A Levoglucosenone-Derived Symmetrical Chiron

christophe Morin

Laboratoire &Etudes Dynamiques de la Structure et de la !Zlectivit& associe au Cnq Chimie Recherches, B&iment 52, Universiti de Grenoble, 38402 St Martin d’H&res (Prance).

Abstract : la&~. a readily mdable pyrolysis product of culhthe. has been wmvuied to e symmehcd ailylic bis chlolilydrin.

Molecules having C2 symmetry are of current interest for their synthetic applications t; in this note, a

method for converting a readily available pyrolysis product of cellulose into a chiron of C2 symmetry is disclosed.

Levoglucosenone, 1 2-4, can be conveniently obtained by simple pyrolysis of cellulose 5-to. Medium

Performance Liquid Chromatography I ’ has been found to be particularly useful for the purification of the crude

pyrolysate, thus allowing rapid isolation at the bench of gram quantities of pure 1 12. Considering the broken line

drawn on its formula, it can be seen that -am timctional group manipulations could in principle yield a functionalixed C2 symmetrical synthon.

Cl

Since stereoselective reduction of the carbonyl group of 1 was known l3 to afford almost quantitatively

the alcohol 2, this became an appropriate starting point for our purpose. Hydrolysis of 2 (0.5 M HCl, 100 OC, 40 min) afforded an hernia&al but, as selective chlorination of its primary hydroxyl group failed, protection

(acetone, CuSO4,15 days) was introduced to give 3 . Chlorination ( CCl4, (C@5)3P, pyridine, RT, 2 h) now proceeded smoothly and produced, after deprotection of the acetal (Dowex 50W X8, THF -H20,60 “C, 8 h ),

thedesired chloride 4. Reduction of the aldehyde (excess NaBH4, -2O’C. pH adjustment to 7 before isolation), followed by

selective tosylation I4 of the primary hydroxyl group ( 1.2 equiv. TsCl, pyr, -20 “C), and displacement by

chloride (IO equiv. LiCl , DMF, Ar, 90 OC, 7 h ) gave 5 . It is of interest to note that despite the cis configuration of the double bond, no pyran derivatives, from internal displacement of the tosylate, could be observed.

As expected from its symmetry, 5 displayed only three lines in its 13C -nmr spectrum l5 . The good

overall yield of this synthesis ( over 45 46 from 1) and the ready availability of levoglucosenone t2 make this

appmachtoaC2 I6 chiron particularly amactive.

5096

0

pyrolysis 0

Cellulose

- Fj NaBH4 \ see

0 90%

1 1) HCI 34% I 2) acetone

Cl

5

REFERENCES AND NOTES 1. Whites&, J.K.; Chem Reu, 1989, 89, 1581-1590.

2. IMpem. Y.: Riffer, R.; Broido, A.; J. Org. Chem, 1973, 38, 204-209.

3. Shatizmleh. E; Pun A& Gem, 1983,55,705-720.

4. Shibagaki, M.; ‘Ihk&&i. K.. Kuao, H.; Honda, 1.; Matsuhita, H.; Chem Lcncrs. 19!&307-310.

5. Shafizedeh, E; Chin, P&S.; Carbah@ Rev.. 1977, 58. 79-87.

6. Brimmxmbe, J.S.; Hunedy, F.; Mather, A.M.: Tuckex, LC.N.; Carbohyi~ Res., 1979, 68, 231-238.

7. Bhate, p.; Horton. D.; Carhoh~~ Res., 1983, 122, 189-199.

8. Fomeaux, R.H.; Mason, J.M.; Mila, I.J.; J. Chem Sot., Perkin Items 1, , 1984, 1923-1928.

9. Mori, hi.; Chuman, T.; Kate, K.; Curb&# Res., 1984, 129, 73-86.

10. Rossinskaya, GA.; Dobele, G.V.; Domburg, GE.; Khim Dmc, 1986. 73-76.

11. Mofin, c.; J. them Juuc.. 1988.65.903~904.

12. Cellulose, p&i=ted with phosphoric acid (3 46 w/w), was pyrolyzed ( 270 ‘C. 10 kR ) for 20 minutes, affer W~~IQ the

cade pyroiysate with aqueous sodium bicarbou&. MPLc(seeref. II) onsilicl~C1H(lSnmparticles~)wurpaf~.

Ehth with dichloromthme afforded pure 1 without the oeed for further pmificatioo in ca 4 % yield (which is within the

range of litemture oaea : see ref. S-9); the whole process t&a only 2-3 boors.

13. Sbafizadeh, F.; F-ux, R.H.; Stevenson, T.T.; Gz&ohJ& Res., 1979, 71, 169-191.

14. Inoonhasttootherin~,this~lpte_toomgiletohechrrrcterizadmdwrsi~yua4dwithout

pmificlltion.

15. 5 : colorless oil, [a] D 25 - 13’ (c =1.9, CHC13). 13C-mm (75 Mhz, CDC13): 132.2 (C-3 and C-4). 68.4 (C-2 aud C-5).

49.1 (C-l and C-6). ‘H-mm (300 MHz- CDC13 ) : an ABMX system with B cellte& at 5.65.4.7 and 3.55 ppm; upon

irmdiation of the 4.7 ppm xsommce, this colw to a singlet for the vinylic protons and an AB sytem for tbe methylenes.

16. For related chirons md synthstic appliationos see inter alia : Kuzmum, J.; Sohu. R: Ca&&ix Res..l968. 83, 63-72.

K611.P.; Kopf, J.; Metzger, J.O.; Schwarting, W.; Gelting, M.; Liebigs Ann Char .1987, 199-204. Doruult,A.;

Trmcbepin,I.; my, J.-C.; synthrsis, 1987.491-493. Mbchinylcl, N.: Kiluyashi. C.; T&rahadrun Lcrr. 1998,31,3637-

3640. ; Kemmerer. J.; R&J. G.; Rinzbach, H.; Angm Chux, lnr. Ed Ei@, 1998.29, 1038-1040. Ekano. S.; Iwbuchi. Y.

Ogasawara, K.; J. Chun Sot., Chem Commun., 1991,820- 821. Machinqa. N.; Kibayrshi, C.; synthesis. 1992,989-994.

Mmzi, M.: Minetti. P.; Misiti. D.: Tcrrahadron, 1992,48. 10127-10132.

(Received in France 28 April 1993; accepted 16 June 1993)