Recent Advances in the Catalytic Cycloaddition of 1,n-Dipoles

Reporter: XiaoBo

Supervisor: Prof. Huang

Noncatalytic 1,4-Dipolar Cycloaddition

New York, 1969; p 223.

E. Chem. Ber. 1967, 100, 1094− 1106.

INTRODUCTION

EXAMPLES：

Donor−Acceptor Cyclobutanes

γ-Methylidene-δ-valerolactones

Vinyl Benzoxazinanones

Allenoates

Generation of 1,n-Dipoles from D–A Cycloalkanes

Angew. Chem., Int. Ed. Engl. 1980, 19, 813−814.

Chem. Rev. 2003, 103, 1151−1196.

DONOR−ACCEPTOR CYCLOBUTANES

Lewis Acid-Catalyzed [4 + 2] Cycloadditions of D–A

Cyclobutanes and Aldehydes

J. Am. Chem. Soc. 2009, 131, 14202−14203.

DONOR−ACCEPTOR CYCLOBUTANES

Stereoselective 1,4-Dipolar Cycloadditions of D–A Cyclobutanes

Org. Lett. 2010, 12, 4732−4735.

Org. Lett. 2011, 13, 1528−1531..

DONOR−ACCEPTOR CYCLOBUTANES

Synthesis of (±)-Akuammicine via [4 + 2] Cycloaddition

of D–A Cyclobutane

Angew. Chem., Int. Ed. 2017, 56, 3055−3058.

DONOR−ACCEPTOR CYCLOBUTANES

1,4-Dipolar Cycloadditions of Modified D–A Cyclobutanes Org. Lett. 2010, 12, 4736−4738.

Org. Lett. 2011, 13, 1528−1531.

Chem. Commun. 2014, 50, 1668−1670.

DONOR−ACCEPTOR CYCLOBUTANES

Generation of 1,4-Dipoles from γ-Methylidene-δ-valerolactones

Chem. Soc. Jpn. 2012, 85, 931−939.

γ-Methylidene-δ-valerolactones

[4 + 3] Cycloadditions of γ-Methylidene-δ-valerolactones Org. Lett. 2009, 11, 5642−5645.

γ-Methylidene-δ-valerolactones

[4 + 2] Cycloadditions of γ-Methylidene-δ-valerolactones J. Am. Chem. Soc. 2008, 130, 16174−16175.

J. Am. Chem. Soc.2010, 132, 7508−7513.

Org. Lett. 2012, 14, 2410−2413.

γ-Methylidene-δ-valerolactones

[4 + 1] Cycloaddition of γ-Methylidene-δ-valerolactones

Chem. Lett. 2009, 38, 204− 205.

γ-Methylidene-δ-valerolactones

[6 + 3] Cycloadditions of γ-Methylidene-δ-valerolactones Org. Lett. 2009, 11, 5642−5645.

γ-Methylidene-δ-valerolactones

[4 + 2] Cycloadditions of Vinyl Oxazinanones Angew. Chem., Int. Ed. 2016, 55,2200– 2204

Vinyl Benzoxazinanones

Palladium(0)-Catalyzed [4 + 2] Cycloaddition of Vinyl

Benzoxazinanones and Isatins Org. Lett. 2017, 19, 3219– 3222

Vinyl Benzoxazinanones

[4 + 1] Cycloaddition of Vinyl Benzoxazinanones and Sulfur Ylides

Nat. Commun. 2014, 5, 5500– 5510

Vinyl Benzoxazinanones

1,n-Dipolar Species from Allenoates

Allenoates

Tetrahedron Lett. 1997, 38, 3461– 3464

Phosphine-Catalyzed [4 + 2] Cycloaddition of Allenoates and Imines

Allenoates

J. Am. Chem. Soc. 2003, 125, 4716– 4717

J. Am. Chem. Soc. 2007, 129, 12632– 12633

Summary

The use of transition metal, Lewis acid in 1,n-dipolar

cycloaddition triggers the reaction by generating the 1,n-

dipoles and provides the opportunity to achieve regio- and

stereoselective transformations.

The development of atypical 1,n-dipolar cycloadditions will

continue to be a leading area in synthetic chemistry toward

functional cyclic compounds and natural products.

Thanks a lot.