A new synthesis of primary aliphatic amines by N,N-didebenzylation. Synthesis of a pirmenol (CI-845) metabolite

Purchase, Claude F.; Goel, O. P.

doi:10.1021/jo00001a090

Cited by 18 publications

(9 citation statements)

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“…However, aqueous base first removed the N-acyl group, and the resulting oxazolidinone anion was refractory to decarbonylation. Hydrogenolysis of the benzylamino bond was highly sensitive to the batch of Pd-C catalyst, 14 but debenzylation has now been found to occur readily and repeatably with the Pearlman palladium hydroxide on carbon catalyst with ammonium formate 24 (hydrogen source) in MeOH/H 2 O at reflux. Finally, the 3′-amino-3′-deoxynucleosides were purified by Dowex 1 × 2 (OH -) chromatography and recrystallized to give 6a and 6b.…”

Section: Resultsmentioning

confidence: 99%

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹

et al. 2001

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Protection (O5') of 2',3'-anhydroadenosine with tert-butyldiphenylsilyl chloride and epoxide opening with dimethylboron bromide gave the 3'-bromo-3'-deoxy xylo isomer which was treated with benzylisocyanate to give the 2'-O-(N-benzylcarbamoyl) derivative. Ring closure gave the oxazolidinone, and successive deprotection concluded an efficient route to 3'-amino-3'-deoxyadenosine. Analogous treatment of the antibiotic tubercidin [7-deazaadenosine; 4-amino-7-(beta-D-ribofuranosyl)pyrrolo[2,3-d]pyrimidine] gave 3'-amino-3'-deoxytubercidin. Trifluoroacetylation of the 3'-amino function, elaboration of the heterocyclic amino group into a (1,2,4-triazol-4-yl) ring with N,N'-bis[(dimethylamino)methylene]hydrazine, and nucleophilic aromatic substitution with dimethylamine gave puromycin aminonucleoside [9-(3-amino-3-deoxy-beta-D-ribofuranosyl)-6-(dimethylamino)purine] and its 7-deaza analogue. Aminoacylation [BOC-(4-methoxy-L-phenylalanine)] and deprotection gave puromycin and 7-deazapuromycin. Most reactions gave high yields at or below ambient temperature. Equivalent inhibition of protein biosynthesis in a rabbit reticulocyte system and parallel growth inhibition of several bacteria were observed with the 7-aza/deaza pair. Replacement of N7 in the purine ring of puromycin by "CH" has no apparent effect on biological activity.

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Section: Resultsmentioning

confidence: 99%

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹

et al. 2001

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“…Diglyme provided an excellent conversion (97−99%) in 18−20 h at 130−135 °C (entries 8,9). Use of these reaction conditions for N-alkylation of secondary amines has been reported . After further optimization the amount of BADMA required was lowered to 1.2 equiv.…”

Section: Resultsmentioning

confidence: 99%

Development of an Efficient Process for the Preparation of Sch 39166: Aziridinium Chemistry on Scale

Gala¹,

Dahanukar²,

Eckert³

et al. 2004

Org. Process Res. Dev.

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“…In a flask equipped with a Dean−Stark trap, a solution of 4-chlorobutyrophenone (3.00 g, 16.4 mmol), ethylene glycol (1.56 g, 25.1 mmol), and p -toluenesulfonic acid monohydrate (312 mg, 1.64 mmol) in benzene (55 mL) was stirred at 90 °C for 18 h. The reaction mixture was cooled to 23 °C and diluted with ethyl acetate (100 mL). The solution was washed with 10% Na 2 CO 3 (30 mL), water (30 mL), and brine (30 mL), then dried (Na 2 SO 4 ), and concentrated in vacuo to give 3.70 g (99%) of ketal 45 as a yellow solid …”

Section: Methodsmentioning

confidence: 99%

“…Calcd for C17H21NO2‚ 0.7H2O: C,71.86;H,7.96;N,4.93. Found: C,71.99;H,7.57;N,4.48. 3-[(2-Hydroxy-2-phenylethyl)(phenylmethyl)amino]-1phenyl-1-propanone (34). To a solution of 2-benzylamino-1-phenylethanol (5.00 g, 22.0 mmol) and N,N-diisopropylethylamine (4.23 g, 32.7 mmol) in THF (150 mL) was added 3-chloropropiophenone (3.70 g, 22.0 mmol).…”

Section: -Hydroxyl-15-diphenyl-1-pentanone (27)mentioning

confidence: 99%

Stereocontrol between Remote Atom Centers in Acyclic Substrates. Anti Addition of Hydride to 1,5-, 1,6-, and 1,7-Hydroxy Ketones

et al. 1998

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For conformationally unconstrained, acyclic organic compounds, the control of stereogenic centers at remote positions of a chain, that is, at a distance of four or more atom centers, remains a challenging problem in asymmetric synthesis. We report on our studies of 1,5, 1,6, and 1,7 diastereoselectivity in hydride reductions of acyclic hydroxy amino ketones and related compounds, which were sparked by our discovery of high 1,5 diastereocontrol (>10:1) with substrates such as 17 and 23. We have been able to achieve both high 1,5- and 1,6-anti diastereocontrol in the reduction of 1,5- and 1,6-hydroxy ketone substrates, respectively. However, the level of 1,7-anti diastereocontrol with 1,7-hydroxy ketones was only moderate. More specifically, reduction of 23 to 24 with R-alpine-hydride or Zn(BH4)2 in CH2Cl2 (predominantly) at −78 °C gave high 1,5-anti stereoselectivity (anti/syn = 10:1 or 13:1, respectively), and reduction of 34 to 35 with R-alpine-hydride (CH2Cl2) gave high 1,6-anti selectivity (anti/syn = 12:1, respectively), whereas reduction of 46 to 44 with R-alpine-hydride (CH2Cl2) gave only moderate 1,7-anti stereoselectivity (anti/syn = 3:1). Results for reductions of 1,5- and 1,6-hydroxy ketone substrates having the N-benzyl structural subunit replaced (i.e., 27 → 28, 29 → 30, 31 → 32, 52 → 53, 54a → 55a, 54b → 55b, 54c → 55c, and 56 → 57) clearly indicate that the stereoelectronic character of this subunit plays a critical role in the attainment of high anti asymmetric induction. Thus, while we obtained exceptionally high 1,6-anti stereoselectivity in the reduction of the N-mesitylmethyl substrate, 54c, to 1,6-diols 55c (anti/syn = 22:1) with R-alpine-hydride at −78 °C in CH2Cl2, the N-methyl substrate, 54b, gave a relatively modest anti/syn ratio of 3:1. The diminished anti/syn ratio of 4:1 in the R-alpine-hydride reduction of methoxy amino ketone 50 to 51 also indicates the importance of the free hydroxyl group for attaining high 1,6-anti stereoselectivity. To rationalize the high remote anti stereocontrol in such acyclic systems, we discuss a chelation-controlled mechanism, involving external hydride addition to a bicyclic metal complex with a coordinated ketone carbonyl (e.g., 33) vs internal hydride addition to a monocyclic metal complex with an uncoordinated ketone carbonyl (e.g., 58).

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A new synthesis of primary aliphatic amines by N,N-didebenzylation. Synthesis of a pirmenol (CI-845) metabolite

Cited by 18 publications

References 0 publications

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹

Development of an Efficient Process for the Preparation of Sch 39166: Aziridinium Chemistry on Scale

Stereocontrol between Remote Atom Centers in Acyclic Substrates. Anti Addition of Hydride to 1,5-, 1,6-, and 1,7-Hydroxy Ketones

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A new synthesis of primary aliphatic amines by N,N-didebenzylation. Synthesis of a pirmenol (CI-845) metabolite

Cited by 18 publications

References 0 publications

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair1

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair1

Development of an Efficient Process for the Preparation of Sch 39166: Aziridinium Chemistry on Scale

Stereocontrol between Remote Atom Centers in Acyclic Substrates. Anti Addition of Hydride to 1,5-, 1,6-, and 1,7-Hydroxy Ketones

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Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹

Syntheses of Puromycin from Adenosine and 7-Deazapuromycin from Tubercidin, and Biological Comparisons of the 7-Aza/Deaza Pair¹