Puromycin. Synthetic Studies. IX. Total Synthesis

Baker, B. R.; Schaub, Robert E.; Joseph, Joseph P.; Williams, James H.

doi:10.1021/ja01606a003

Cited by 80 publications

(23 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The upward mutarotation, [a]n23 -147.4" (2 minutes), + -113" (20 minutes, final; c, 0.5 in water) alllowed the assignment to X I of p-configuration. The equilibrium rotation value of X I agreed well with that given in the literature ( [ a ]~ -112", in water), although a inutarotation had not been recorded previously (4).…”

Section: S-a1lzino-3-deoxy-p-~-arabinose Hydrochloride ( X I )supporting

confidence: 90%

See 1 more Smart Citation

The Methyl 3-Nitro-3-Deoxy- And 3-Amino-3-Deoxy-Arabinopyranosides

Baer¹,

Ahammad²

1963

Can. J. Chem.

View full text Add to dashboard Cite

The nitromethane cyclization of L'-methoxy-diglycolic aldehyde was shown t o furnish methyl 3-nitro-3-deoxy-a-L-arabinopyranoside and methyl 3-nitro-3-deoxy-p-D-arabinopyranoside as coproducts of the previously obtained p-D-ribo isomer. As expected, the enantiomorphic dialdehyde, D'-methoxy-diglycolic aldehyde, afforded the corresponding WD-and P-L-arabino derivatives in addition to the 6-L-ribo isomer. Catalytic hydrogenation of the four new nitroglycosides gave the corresponding aminoglycoside hydrochlorides. The 3-amino-3-deoxy-D-and L-arabinose hydrochlorides were obtained from their glycosides by hydrolysis and crystallized as mutarotating p-forms.The spontaneous epimerization, in aqueous solution, of aci-nitropentoside sodium salts was investigated.In the cyclization (I), with nitromethane and sodium methoxide, of L'-methoxydiglycolic aldehyde (I) a methyl aci-nitrodeoxy pentoside sodium salt had been isolated in crystalline condition in a yield of about 40%. This salt had been shown to possess formula I1 and must therefore be denoted as methylRlanifold experiences gathered subsequently in similar nitromethane condensations and recorded in papers of this series have borne out the hardly surprising fact that this type of reaction does not proceed in a stereospecific way, although a notable stereoselectivity is always observed. I t was of interest, therefore, to investigate whether, and to which extent, stereoisomers of I1 were formed in the reaction which produced the latter as the apparent main product. The three possible stereoisomers of I1 which might arise from the dialdehyde I are the corresponding a-L-threo (111), P-D-threo (IV), and a-L-erythro (V) 3-deoxypentose derivatives. The present study was-intended, furthermore, to uncover the cause of the previously~observed mutarotation of 11; i.e. to verify in the pentose series that glycoside nitronates in solution are liable to undergo spontaneous epimerizations, as has been found to be the case with nitronates derived from hexosides (2, 3).We are now able to demonstrate that when dialdehyde I is cyclized with nitromethane, the a-L-threo and P-D-threo forms of methyl 3-aci-nitro-3-deoxypentopyranoside sodium (I11 and IV, respectively) indeed occur in the reaction mixture as minor components beside the chief product, p-D-erythro salt 11. Although the salts I11 and IV could not be isolated as such, their presence was indicated by the isolation of two new, free nitroglycosides that arose upon deionization of the mixture. Thus, methyl 3-nitro-3-deoxy-a-L-arabinopyranoside (VI), originating from 111, and methyl 3-nitro-3-deoxy-P-D-arabinopyranoside (VII), arising from IV, were obtained in yields of approximately 5% each.These crystalline nitroglycosides were hydrogenated to furnish the corresponding aminoglycosides, which crystallized as hydrochlorides: methyl 3-amino-3-deoxy-a-L-arabinopyranoside hydrochloride (VIII) and methyl 3-amino-3-deoxy-0-D-arabinopyranoside

show abstract

Section: S-a1lzino-3-deoxy-p-~-arabinose Hydrochloride ( X I )supporting

confidence: 90%

“…Proof of the structure and configurations of VIII and I X was afforded by acid hydrolysis yielding reducing amino sugars. Glycoside I X gave 3-amino-3-deoxy-D-arabinose hydrochloride (XI), which has been described by Baker, Schaub, and Williams, (4). We obtained an upward-mutarotating /3-form ([alD -147' -+ -113').…”

mentioning

confidence: 82%

The Methyl 3-Nitro-3-Deoxy- And 3-Amino-3-Deoxy-Arabinopyranosides

Baer¹,

Ahammad²

1963

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…(Ic) Methyl 2-0-methanesulfonyl-a-D-xylofuranoside (11) (70 g, 0.29 mole; obtained from 58.5 g of methyl 3,s-0-isopropylidene-a-D-xylofuranoside) was dissolved in absolute methanol (140 ml) and cooled to 0'. To the stirred solurion was added freshly prepared 2 M merhanolic sodium merhoxide (158 ml, 0.316 mole) at such a rate that the temperature was maintained at 0'.…”

Section: Methyl ~~-A I I / I~~~o -~-D -~~X O J~i ' C Imentioning

confidence: 99%

Anomeric deoxy and unsaturated methyl pentofuranosides and pentopyranosides

Lemieux¹,

Watanabe²,

Pavia³

1969

Can. J. Chem.

View full text Add to dashboard Cite

Both the anomers for methyl 2,3-dideoxy-D-glycero-pent-2-enofuranoside were characterized and hydrogenated to the corresppnding methyl 2,3-dideoxy-D-glycero-pentofuranosides. The similar compounds were prepared in the pyranoside ring form but in the L-glycero configuration. The anomeric forms for methyl 3-deoxy-L-erytlrro-pentopyranoside are reported together with a number of their derivatives of interest for the study of solvation effects on conformational equilibria (21). The molar rotations of the deoxy and unsaturated glycosides are discussed as are the conformational properties of the various compounds.Canadian Journal of Chemistry, 47, 4413 (1969) In a previous communication (I), the preparation of the four stereoisomeric methyl 4,6-0-benzylidene-2,3-dideoxy-D-hex-2-enopyranosides was accomplished, in each case, by opening of the epoxide ring of a parent 2,3-anhydro derivative to the corresponding iodohydrin which was treated with either p-toluenesulfonyl (tosyl) or methanesulfonyl (mesyl) chloride in pyridine. We wish to report a modified procedure which allowed the preparation of the anomeric forms both for methyl 2,3-dideoxy-D-glycero-pent-2-enofuranoside (4c and 9c) and for methyl 2,3-dideoxy-L-glycero-pent-2-enopyranoside (17c and 18c).Methyl 5-0-benzoyl-2,3-dideoxy-P-D-glyceropent-2-enofuranoside (9a) was first prepared by reaction of 3,5-di-0-benzoyl-D-erythro-pent-1-enofuranose with methanol (2). The p-D-configuration was later assigned by an alternative synthesis (3,4) involving reduction of methyl 5-0-benzoyl-2,3-di-0-tosyl-P-D-ribofuranoside by the method of Tipson and Cohen (5). The physical constants and nuclear magnetic resonance (n.m.r.) spectrum reported for 9a indicate that this compound was not pure. Also, the n.m.r. signal for Hz was erroneously assigned to HI. It is of interest to note that several 2',3'-unsaturated nucleosides have been prepared (6-10).The 5-0-benzoyl derivative (la) of the readily available methyl 2,3-anhydro-a-D-lyxofuranoside (I 1) was treated with sodium iodide in acetone in the presence of acetic acid and sodium acetate as described previously (1). The spectrum of the sirupy product (2a) required high purity. That the epoxide opening followed the normal course (attack at the 3-position) for a 2,3-anhydrofuranoside (12,13) was established by benzoylation of the iodohydrin 2a to 2c followed by hydrogenolysis to yield crystalline methyl 2,5-di-0-benzoyl-3-deoxy-a-D-theo pentofuranoside (3). This 3-deoxy structure was required since the anomeric proton (singlet at r 4.85) was not appreciably coupled to either of the methylene protons at r 7.35 and 8.05. The quartet at .r 5.35 was assigned to Hz and the spacings indicated 6.5 Hz coupling with the methylene proton (H,) at r 7.35, and 1.6 Hz coupling with that (H,) at r 8.05. Spin decoupling also showed the methylenic protons to be coupled with a signal forming part of a multiplet (H4, H,, and H,,) centered at r 5.5 and assigned to H,.Following the previously reported procedure for the reduction of iodohydrins to olef...

show abstract

“…The residue was dissolved in CHC13 , washed with sat. NaHC0 3 (10). A mixture of9 (620.7 mg, 1.57 mmol) and NaOMe (Na, 361mg, 15.7mmol) in MeOH (40ml) was stirred at room temperature for 20hr.…”

Section: -Dime Thylamino-9-(2' -Deoxy-3' 5' -Di-0-benzo Yl-{3-d-mentioning

confidence: 99%

“…The coupling constants of the proton signals of 1, 2 and some intermediates are shown in Table I. Especially, the difference in f 2 ·p, 3 • values of the proton signals of 1 and some 2' -deoxynucleosides could suggest the puckering of the ribose ring. 21 ) It could be supposed that such puckering of the ribose ring would cause a change in orientation of the aminoacyl moiety of puromycin (1) and influence the recognition by a peptidyl transferase and its biological activity.…”

mentioning

confidence: 99%