Kinugasa β-内酰胺合成反应

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手性有机铜(手性恶唑啉)催化剂催化下,端基炔和硝酮进行偶极环加成得到异恶唑啉中间体,重排后得到立体选择性的β-内酰胺反应


反应机理


反应实例

(3S, 4S)-1,3,4-Triphenyl-2-azetidinone (5). (S)-trisoxazoline 6 (11.3 mg, 0.03 mmol) and Cu(ClO4)2.H2O (9.3 mg, 0.025 mmol) in 4 mL MeCN were stirred for 2 h at 15 C. After cooling to 0 C, dicyclohexylamine (0.25 mmol) was added, followed after 10 min by phenylacetylene 1 (38 mg, 0.375 mmol). The color turned yellow and 0.25 mmol of nitrone 2 was added. The reaction was monitored by TLC and after 35 h the mixture was first filtered over silica gel using DCM as eluent and the solvent evaporated. Flash chromatography (PE/DCM) gave b-lactam 5 in 56% yield,[a]20 D ¼ 8.0 (c ¼1.62, CHCl3) and 82%ee.

【Tang Y, J Org Chem, 2006, 71, 3576】


相关文献

1 Kinugasa M J Chem Soc Chem Comm 1972 466

2 Fu GC J Am Chem Soc 2002 124 4572

3 Basak A Tet Lett 2002 43 5499

4* Fu GC Angew Chem Int 2003 42 4082

5 Marco-Contelles J Angew Chem Int 2004 43 2198

6* Tang Y J Org Chem 2006 71 3576

7* Guiry PJ Tet Asymm 2007 18 199

8 Basak A Synlett 2007 2321

9 Sibi MP Chem Rev 2008 108 2887

10 Hsung RP Org Lett 2008 10 3477

11* Saito T Tet Lett 2009 50 4969

12 Pezacki JP Tet Lett 2009 50 1893


编译自:Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 259.


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