Cycloaddition reactions in synthesis

Whereas there are numerous examples of the application of the products from diastereoselective 1,3-dipolar cycloaddition reaction in synthesis [7, 8], there are only very few examples on the application of the products from metal-catalyzed asymmetric 1,3-dipolar cycloaddition reaction in the synthesis of potential target molecules. The reason for this may be due to the fact that most metal-catalyzed asymmetric 1,3-dipolar cycloaddition reaction have been carried out on model systems that have not been optimized for further derivatization. One exception of this is the synthesis of a / -lactam by Kobayashi and Kawamura [84]. The isoxazoli-dine endo-21h, which was obtained in 96% ee from the Yb(OTf)3-BINOL-catalyzed... 

The last comprehensive survey of this area dates back to 1984, when the two-volume set edited by Padwa, 1,3-Dipolar Cycloaddition Chemistry, appeared. Since then, substantial gains in the synthetic aspects of this chemistry have dominated the area, including both methodology development and a body of creative and conceptually new applications of these [3+ 2]-cycloadditions in organic synthesis. The focus of this volume centers on the utility of this cycloaddition reaction in synthesis, and deals primarily with information that has appeared in the literature since 1984. Consequently, only a selected number of dipoles are reviewed, with a major emphasis on synthetic applications. Both carbonyl ylides and nitronates, important members of the 1,3-dipole family that were not reviewed previously, are now included. Discussion of the theoretical, mechanistic, and kinetic aspects of the dipolar-cycloaddition reaction have been kept to a minimum, but references to important new work in these areas are given throughout the 12 chapters. 

Diels-Alder cycloaddition reactions in synthesis of natural heterocycles 87AHC(42)245. 

ACIEE 1984, 23,876 ACJEE 1977, 16, 10 Organic Reactions 1984, 32, 1 W. Carruthers Cycloadditions Reactions in Organic Synthesis (Pergamon Press, Oxford) 1990... 

Cycloaddition Reactions in Organic Synthesis. 1 Edited by S. Kobayaslii and K. A. Jorgensen Copyright 2001 Wiley-VCH Verlag GmbH ISBNs 3-527-30159-3 (Hardcover) 3-527-60025-6 (Electronic)... 

This methodology has been used for the synthesis of the C3-C14 segment 24 of the antitumor agent laulimalide 23 (Scheme 4.22) [35]. The constrained chiral BOX ligand 21c in combination with Cu(OTf)2 afforded dihydropyrane 6f by a cycloaddition reaction in good yield and ee this was converted to the C3-C14 segment 24 via a Ferrier-type rearrangement in several steps. 

See e.g. (a) W. Cahhuthehs, Cycloaddition Reactions in Organic Synthesis, Tetrahedron Organic Chemistry Series Vol. 8 Pergamon Press Elmsford, NY 1990 (b) I. OjiMA, Catalytic Asymmetric Synthesis, VCH Publishers. Inc. New York. 1993 ... 

Shu Kobayashi Karl Anker Jorgensen (Eds.) Cycloaddition Reactions in Organic Synthesis... 

CARRUTHERS Cycloaddition Reactions in Organic Synthesis GAWLEY AUBE Principies of Asymmetric Synthesis HASSNER STUMER Organic Syntheses based on Name Reactions and Unnamed Reactions... 

Carruthers, W., Cycloaddition Reactions in Organic Synthesis, Tetrahedron Organic Chemistry Series, Vol. 8, Baldwin, J. E., and Magnus, P. D., eds., Pergamon Press, 1990. 

The introduction of heterodienes has extended the synthetic versatility of cycloaddition reactions in organic synthesis.150 Denmark and coworkers have developed the use of nitroalkenes as dienes in [4+2] cycloaddition. Nitroalkenes react with simple alkenes in the presence of SnCl4 as a promoter. For example, the reaction of nitrocyclohexene with cyclopentene gives three products. The major product is awh-isomer, which arises from an exo approach of cyclopentene toward nitrocyclohexene (see Eq. 8.94).151... 

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