Aza-Prins Cyclization

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Presentation transcript:

Aza-Prins Cyclization 陈殿峰 2011.01.15

Contents ♦ Introduction ♦ Catalyzed Aza-Prins ♦ Cascade Reactions ♦ Conclusions

Introduction Prins Cyclization 1.Condensation of olefins&aldehydes 2.Kriewitz, 1899 8.Aza-Prins Prins Cyclization 3.Prins, 1917 7.Homoallylalcohol 4.Simple olefins 6.Diene 5.Substituted olefins E. Arundale; L. A. Mikeska. Chem.Rev. 1952.505-550. David.R. Adams. Synlett. 1977.661-672.

Catayzed Aza-Prins Cyclization HOAc p-TSA CSA…… Brønsted acids Catalysts Au Fe B …… Lewis acids

General model

Brønsted Acid J.S.Yadav. J. Org. Chem. 2010.75. 2081-2084. BA: HOAc, CSA,,TsOH p-TSA, PMA J.S.Yadav. J. Org. Chem. 2010.75. 2081-2084.

Brønsted Acid Aza-Prins or Cope? Indirect evidence : Adrian P. Dobbs. Org. Biomol. Chem.,2010,8,1064-1080

Lewis Acid 1、Au catalysts Poor conversion: AgBF4 AgOTf 4b: more electrophilic 2,6-DBP: 2,6-di-tert-butylpyridine Young Ho Rhee. J. Am. Chem. Soc. 2009. 131. 14660-14661.

1、Au catalysts Young Ho Rhee. J. Am. Chem. Soc. 2009. 131. 14660-14661.

1、Au catalysts Two possible pathways: slow unstable Evidence for Young Ho Rhee. J. Am. Chem. Soc. 2009. 131. 14660-14661.

2、Fe catalysts R. P.Hsung .Org.Lett. 2006.8.3837-3840. X=Cl、Br、I、acac Energy Calculation Proposed Intermediates R. P.Hsung .Org.Lett. 2006.8.3837-3840. Juan I. Padron. Eur.J.Org.Chem. 2010. 2304-2313.

2、Fe catalysts Solvents screen： CH2Cl2 is the best！ R. P. Hsung .Org.Lett. 2006.8.3837-3840.

3、Bi catalysts 4、Ga catalysts R’=alkyl,82-90% ; R’=aryl, ＞90%; dr=9:1 M. S. R. Murty. Tetrahedron.Lett. 2008.49.1141-1145. 4、Ga catalysts R=alkyl or aryl; Yield 80-92% dr＞96：4 No GaI3, no reaction; Only GaI3, yield 20-35% S. J. Yadav. Tetrahedron.Lett. 2008. 49. 3330-3334.

I2 catalysts J. S. Yadav. Tetrahedron.Lett. 2009.50.2256-2260. HTIB: PhIOH(OTs) DIB :PhI(OAc)2 J. S. Yadav. Tetrahedron.Lett. 2009.50.2256-2260.

Other Lewis Acids: Sc 、In 、Sn、 Ti etc. also performed well. I2 catalysts Mechanism： Stereocontrol： J. S. Yadav. Tetrahedron.Lett. 2009.50.2256-2260. Other Lewis Acids: Sc 、In 、Sn、 Ti etc. also performed well. Adrian P. Dobbs. Org.Biomol.Chem.,2010,8,1064-1080

5、Boron catalysts yield:68-93% R=aryl, mainly cis products Substituted amine failed! J. S. Yadav. Tetrahedron.Lett. 2010.51.1578-1581.

Cacade Reactions 1、Formal double Aza-Prins 2、Aza-Prins-Pinacol 3、Aza-Prins-Friedel-Crafts 4、Diels-Alder-Aza-Prins

1、Formal double Aza-Prins X= O / NTs X= O / NTs J. S. Yadav. Tetrahedron.Lett. 2010.51.3412-3416. J. S. Yadav. J.Org.Chem. 2010.75. 2081-2084.

1、Formal double Aza-Prins Mechanism: (1) (2)

1、Formal double Aza-Prins Matthew D. Shair. J.Am.Chem.Soc. 2008.130.16864-16866.

2、Aza-Prins-Pinacol

2、Aza-Prins-Pinacol Mechanism: 1、preferential cyclization of E-imine 2、avoid bulky siloxy group Lary. E. Overman. Org.Lett. 2001.3.1229-1232.

2、Aza-Prins-Pinacol Alan. Armstrong. Org.Lett. 2005.7.1335-1338.

2、Aza-Prins-Pinacol Overman’s conclusion: 1、Ts-iminium tends to be trapped by enolate rapidly 2、PathwayⅠgenerally for N-alkyl iminium L.E. Overman. JACS. 1998.120.4329-4336. Armstrong proposed mechanism Alan. Armstrong. Org.Lett. 2005.7.1335-1338.

3、Aza-Prins-Friedel-Crafts Alkylation John.A. Porco, Jr. J.Am. Chem. Soc. 2010. 132. 6412-6418.

3、Aza-Prins-Friedel-Crafts Alkylation Energy Calculation John.A. Porco, Jr. J.Am. Chem. Soc. 2010. 132. 6412-6418.

3、Aza-Prins-Friedel-Crafts Alkylation With diene: John.A. Porco, Jr. J.Am. Chem. Soc. 2010. 132. 6412-6418.

4、Diels-Alder-Aza-Prins Methyl Homosecodaphniphyllate Clayton H. Heathcock. J. Am. Chem. Soc. 1988. 110,8734-8736. J. Org. Chem. 1992. 57. 2544-2553. K C. Nicolaou. Angrew. Chem. Int. Ed. 2002. 41. 1668-1698

Polystep Reaction Stephen Hanessian. Org. Lett. 2004. 6. 4683-4686 Stephen Hanessian .J. Am. Chem. Soc. 2004. 126. 6064-6071. Stephen Hanessian .J. Org. Chem. 2005. 70, 5070-5085.

Reductive coupling followed by Aza-Prins 1st step: reductive coupling between eneyne Regioselectivity 20:1 Glenn C. Micalizio. Org.Lett. 2009.11.4982-4985.

Reductive coupling followed by aza-Prins Glenn C. Micalizio. Org.Lett. 2009.11.4982-4985.

Aza-Prins followed by Electrocyclic Tohru Fukuyama. J.Am.Chem.Soc. 2010.

Conclusion 1、 Aza-Prins cyclization is a classical methodology in synthesis of a lot of natural products, especially alkloids; 2、To the best of my knowledge, aza-cope rearrangment is always competing with Aza-Prins ,and there is still no effective solution. 3、Few effective catalysts could promot aza-prins crclization behaving in asymmetric ways.

Thank you!