Stereospecific Synthesis of ω-Amino-β-D-furanoribosyl cetic Acid Based on Microwave Assisted ittig-Michael Tandem Reaction†

doi:10.7503/cjcu20131054

Chem. J. Chinese Universities ›› 2014, Vol. 35 ›› Issue (5): 959.doi: 10.7503/cjcu20131054

• Organic Chemistry • Previous Articles Next Articles

Stereospecific Synthesis of ω-Amino-β-D-furanoribosyl cetic Acid Based on Microwave Assisted ittig-Michael Tandem Reaction^†

MA Donglai¹, LI Xiaoliu^1,^*(), HAO Le¹, ZHANG Pingzhu¹, CHEN Hua¹, ZHAO Ying²

1. Key Laboratory of Chemical Biology of Hebei Province, School of Chemistry and nvironmental Science, Hebei University, Baoding 071002, China
2. College of Science, Agricultural University of Hebei, Baoding 071001, China

Received:2013-10-29 Online:2014-05-10 Published:2014-04-12
Contact: LI Xiaoliu E-mail:lixl@hbu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21172051, 21372060), the Key Basic Research Foundation of Hebei Province, China(No.12966417D) and the Natural Science Foundation of Hebei Province, China(Nos.Y2011119, ZH2011110) and the Medicinal Joint Founds of the Natural Science Foundation of Hebei Province and Shijiazhuang Pharmaceutical Group Foundation of China(Nos.B2011201169, B2012201113)

Abstract

Abstract:

An efficient and stereoselective method for synthesizing ω-amino-β-D-furanoribosylactic ester was established based on the microwave assisted Wittig-Michael tandem reaction of acetone protection of D-ribose(2) and Ylide 3(Ph₃P═CHCOOEt), and followed by ω-azidation and reduction. The microwave assisted Wittig-Michael addition reaction was carried out effectively and β-stereoselectively in CH₃CN at 115 ℃ with a yield up to 91% within 10 min, and the α-stereomer could easily converted to the thermodynamically more stable β-stereomer during workup in basic condition. The calculation results of quantum chemistry show that β-isomer 4b is higher than α-isomer 4a in thermodynamic stability. The structures of the compounds were identified by spectral analyses of ¹H NMR, ¹³C NMR and HRMS.

Key words: Amino furanoribosyl acid ester, Microwave assisted reaction, Wittig-Michael tandem reaction

CLC Number:

O629.11

TrendMD:

MA Donglai, LI Xiaoliu, HAO Le, ZHANG Pingzhu, CHEN Hua, ZHAO Ying. Stereospecific Synthesis of ω-Amino-β-D-furanoribosyl cetic Acid Based on Microwave Assisted ittig-Michael Tandem Reaction^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 959.

Figures/Tables 7

Fig.1 Structures of some sugar amino acid derivatives

Ethyl 2-C-(5'-deoxy-5'-amino-D-β-furanoribosyl)-acetate(1)^Reagents and conditions: (1) a. CH3CN, MW, 115 ℃; b. MeONa, MeOH; (2) MsCl, pyridine, 0 ℃; (3) NaN3, DMF, 100 ℃; (4) 12% HCl, EtOH, 10% Pd/C, H2.

Scheme 2 Process of the Wittig-Michael reaction

Table 1 Microwave assisted Wittig-Michael reaction of sugar(2) and Ylide(3)a

Entry	Solvent	Temperature/℃	t/min	Yield(%)	Entry	Solvent	Temperature/℃	t/min	Yield(%)
1	Toluene	135	10	87.5	7	CH₃CN	115	10	91
2	Xylene	160	10	85	8	CH₃CN	115	5	64
3	CH₃OH	100	10		9	CH₃CN	115	15	91
4	CH₃CN	81	10		10	CH₃CN	115	20	89
5	CH₃CN	100	10	60	11	CH₃CN	120	10	81.2
6	CH₃CN	110	10	85	12^b	CH₃CN	Reflux	720	80.5

Scheme 1 Conversion of compound 4a(α-isomer) to compound 4b(β-isomer) under basic condition

Fig.2 Optimized conformations of the isomers of compound 4

Table 2 Energy of the isomers of 4a and 4b*

Isomer	E_total/ eV	E_ele/ eV	E_rep/ eV	10³⁰μ/(C·m)	ΔE_LUMO-HOMO/(kJ·mol^-1)
4a	-22911.27	-56765.82	33854.55	12.55	676.91
4b	-22911.35	-55828.84	32917.49	5.64	701.61

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Stereospecific Synthesis of ω-Amino-β-D-furanoribosyl cetic Acid Based on Microwave Assisted ittig-Michael Tandem Reaction^†

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