April, 1949
CONFIGURATION OF STREPTOSE AND STREPTOBIOSAMINE [CONTRIBUTION FROM THE
Streptomyces Antibiotics. XXII.
RESEARCH LABORATORIES OF MERCK& CO.,
1445
INC.]
Configuration of Streptose and Streptobiosamine
BY FREDERICK A. KUEHL,JR., ROBERTL. CLARK,MARYNEALEBISHOP,EDWINH. FLYNN AND KARLFOLKERS The degradative preparation of dihydrostrepto- acetylthiodihydrostreptobiosaminide by reaction sonic acid lactone and the configuration of strep- with ethyl mercaptan and hydrogen chloride. The tose and streptobiosamine have been communi- crude thioglycoside was reacetylated, and the cated'; the details of these studies and a new product was treated with mercuric chloride and improved preparation of the CHSGHF, CH Dihydrolactone are described herein. streptomycin I The improvement also made R = HCOR I available crystalline tetraa c e t y l di hydrostreptobios- 0 (GHsS)zCH-COH 0 I IHCl amine. CHaOH Although the structural AcoCH CH, I HA - - formula2 of streptobiosI IV amine was determined, cerCHzOAc tain stereochemical aspects HgClz of the structure remained to be elucidated. The configCHOAc y C H O C H 8 uration of the glycosidic I I I HCOR HCOR 1 F H i ' d P ------f AczO linkage between streptose 0 I and N - methyl - L - glucos(AcO)zCH-COH 1 AcOCHzCOH o OHC--COH amine has been calculated3 I 0 I I I CH to be a-Lon the basis of the L C H CH I I I rotations of tetraacetylbisCHs CHs CHI d e s o x y s t r e p t o biosamine4 V VI11 I and its component^.^,^*' I The stereochemical features Ni(H) of streptobiosamine remain7 C H O H ~ C H O A C ing unknown concerned the I streptose moiety, and for the H COR elucidation of this aspect of I the molecule, the lactone I HOCHz-COH -+ AcOCHzCOH and the hydrazide of dihy0 I 0 I C H -----L L C H drostreptosonic acid have I I been prepared t o determine CHI CHs the sign of their optical VI I11 rotations. Methyl pentaacetyldihydrostreptobiosaminide* (I), which is prepared from dihydrostreptomycin, was converted into ethyl penta-
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I
1
(1) Kuehl, Bishop, Flynn and Folkers, THIS JOURNAL, 70, 2613 (1948). (2) Kuehl, Flynn, Brink and Folkers, ibid., 68, 2679 (1946). (3) Lemieux, De Walt and Wolfrom, ibid., 69, 1838 (1947). (4) Kuehl, Flynn, Brink and Folkers, ibid., 68, 2096 (1946): Hooper, Klemm, Polglase and Wolfrom, ibid., 68, 2120 (1946). In the latter reference, this compound is called tetraacetyldidesoxydihydro - L-streptobiosamine. ( 5 ) Brink, Kuehl, Flynn and Folkers. ibid.. 68. 2405 (1946).
HCOH
1 HOCH~--COH I
n
L
(1946). (7) Wolfrom and Thompson, ibid., 69, 1847 (1947). (8) Brink, Kuehl, Flynn and Folkers, ibid., (1946).
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