3798 1-01. so

COMMUNICATIONS T O T H E E D I T O R

REDUCTION OF KETONES WITH DIPHENYLTIN DI- HYDRIDE. A NEW TYPE OF HYDRIDE REDUCTION Sir :

Recently van der Kerk, Luijten and Soltes have reported that organotin hydrides of the type R3SnH (R = phenyl, n-propyl, n-butyl) add readily a t 70-90°, via an apparently non-radical niech- anism, to olefins substituted with groups such as alkyl, aryl, cyano, carbomethoxy, carboxamido, and aryloxy.‘ We attempted to bring about a similar reaction between diphenyltin dihydride and methyl vinyl ketone, reaction (1). However, in wet ether a t room temperature in 13 hours, reaction (2) occurred instead.

(CsH5)zSnHz + CH2=CHCOCH3

(C&)zSn( C H ~ C H Z C O C H ~ Z (1)

(C6H5)2Sn + CH~=CHCHOHCHB (2)

The products were separated easily by virtue of the fact that the yellow diphenyltin which was formed is insoluble in ether. A yield of pure methyl vinyl carbinol was isolated.

In the usual reductions of carbonyl compounds by metal hydrides a metal salt of the alcohol is formed by the addition M - H + R2C=0 --f

RzCHOM. A hydrolysis step is thus necessary in the isolation of the alcohol. The distinctive char- acteristic of the present reaction is that two hydro- gens undergo uncatalyzed2 transfer from tin to the carbonyl group leading directly to the alcohol- no hydrolysis step is required.

Dipheiiyltin dihydride selectively reduces the carbonyl group of a$-unsaturated aldehydes and ketones as suggested by the above and the follow- ing examples. In each case the a,@-unsaturated alcohol was the only product isolated. The yield of pure product is indicated in parentheses: cin- namaldehyde (75Y0), mesityl oxide (GOYo), chalcone (75%), and crotonaldehyde (59%).

Simple carbonyl compounds which have been reduced include cyclohexanone (827,), benzophen- one (5976), and benzaldehyde (62‘5,). Camphor and 2-acetylcyclohexanone, on the other hand, are unaffected by diphenyltin dihydride under the same conditions in two days.

A substantial degree of stereoselectivity in this reduction is revealed by the following results : benzil yields 84% of pure meso-hydrobenzoin ; d-carvone, 83y0 of carveols containing 977, d-cis- carveol (based on optical rotation) ; 4-t-butylcgclo- hexanone, 85% of 4-t-butylcyclohexanoIs contain- ing about 90% trans isomer ; 2-methylcyclohex- anone, 83YG of 2-methylcyclohexanols containing 7801, trans isomer.

Further details on this and other reductions by organotin hydrides will be submitted later.

(1) G. J. M. van der Kerk, J. G Sol tes and J. G A Luiiten, J

( 2 ) Uncatalyzed in the sense tha t a solid hydrogenation catalyst A p p l i e d Ckcm , 7 , 3;26 (1957).

15 not needed

Acknowledgments.-lye wish t:) exprc‘si o x appreciation to the Office of Ordnance Research for support of this research and to the Metal and Thermit Corporation for generous supplies of organotin compounds. DEPARTMENT OF CHEMISTRY USIVERSITY OF KEW HAMPSHIRE HENRY c. KCIVI1.A

OSCAR 1’. BEUMEI., J R . DURHAM, NEW HAMPSHIRE

RECEIVED JUSE 10, 1968

TOTAL SYNTHESIS OF GOSSYPOL

Sir:

Reaction of freshly prepared apogossypo11,2 ( I ) , 2,2‘ - bi - 1,G,7 - trihydroxy - 5 - isopropyl - 3- methylnaphthyl, the very unstable degradation product of gossypol2 (II), with N,N’-diphenylforni- amidine3,4 (CsH5NHCH=h’C6H5) gave a compound identical with dianilinogossypo12s5 (111) prepared from gossypol by the action of aniline, m.p. and

R OH I I

mixed m.p. 302’ (dec.); infrared spectra (KRr) identical. Hydrolysis6,’,* of dianilinogossypol yields gossypol. Apogossypol hexamethyl ether has now been demethylated to apogossypol by the use of boron b r ~ m i d e . ~ Identification was established by infrared (CHC13) comparison arid acetylation of the demethylated product. The latter was identical (infrared and mixed m.p.) with apogossypol hexacetate.’ Since (a) reaction of N,N’-diphenylformamidine with phenols is reported always to introduce the entering group (C~HSN=CH-) ortho to a hydroxyl group3 and (b) the structure of apogossypol and its hexamethyl etherlo has been established by an unambiguous synthesis, the results described comprise a total synthesis of gossypol. The structure of gossypol (11), 2,2’-bi-8-formyl-1,6,7-trihydroxy-5-isopropyl- 3-methylnaphthyl, formulated by Adam9 as ;I

(1) E. P. Clark, J . Biol. Chenz., 78, I59 (11328). ( 2 ) R. Adams, R. C. Morris, T. A. Geissman, D. J. Hutterhaugh

and E. C. Kirkpatrick, THIS JOURNAL, 60, 2193 (1938). (3) J . B. Shoesmith and J. Haldane, J . C h e n . So<., 2704 (192:3),

(4) R. Kuhn and H. A. Staab, Ber., 87, 274 (1954). (5) Kindly supplied b y Drs. A. h l . Altschul and V, L. Frampton,

(6) F. E. Carruth, THIS JUURNAL, 40, 617 (11318). (7) E. P. Clark, J . Biol. Ch?nz., 76 , 279 (1928). ( 8 ) V. IC. Murty, K . S. Murtp and 1’. R. Seshadri, Proc. Iwdian

(9) F. L. Benton and T. E. Dillon, THIS J O U R N A L , 64, 1128 (1942). 110) J D. Edwards, Jr and J. I.. Ca5hxw, i h i d , 79, 21’83

( I ! J i i ) ,

2403 (19%).

Southern Regional Laboratory, E. S. D. A.

A c Q ~ . Sci., A16, 54 (1942).