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Asymmetric 1,3-Dipolar Cycloaddition Reactions Catalyzed by Heterocycle-Based Metal Complexes

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Book cover Heterocyclic Supramolecules II

Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 18))

Abstract

Highly enantioselective 1,3-dipolar cycloaddition reactions of several 1,3-dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and enantioface differentiation. The scope and limitations of each cycloaddition reactions were also briefly described. Of the chiral hererocycle-based ligands, chiral bisoxazoline, 2,6-bis(oxazolinyl)pyridine, and related oxazoline ligands are shown to be quite effective in obtaining high levels of asymmtric induction. The combination of the bisoxazoline ligand derived from (1S,2R)-cis-1-amino-2-indanol and metal salts was especially efficient for asymmetric cycloaddition reactions of a number of 1,3-dipoles, such as nitrones, nitrile oxide, nitrile imines, diazoacetates and azomethine imines. The metals utilized for the heterocycle-based complexes show a crucial role for degree of asymmetric induction depending upon the 1,3-dipole used. High levels of enantioselectivity were achieved in 1,3-dipolar cycloaddition reactions of unstable carbonyl ylides with benzyloxyacetaldehyde derivatives, α-keto esters, 3-(2-alkenoyl)-2-oxazolidinones, and even vinyl ethers, which were catalyzed by Pybox-lanthanoid metal complexes.

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Notes

  1. 1.

    The endo-adduct is defined as the product in which the more important substituent is on the opposite side of the epoxy bridge.

  2. 2.

    (4S,5S)-Pybox-Ph2-Eu(OTf)3 (10 mol%), CH2Cl2, reflux: 89% yield, 44% ee; (4S,5S)-Pybox-Ph2-Yb(OTf)3 (10 mol%), CHCl3, reflux: 71% yield, 45% ee.

Abbreviations

BINIM:

Binaphthyldiimine

Box:

Bisoxazoline

DBFOX:

4,6-Dibenzofuranyl-2,2′-bis(oxazoline)

DIEA:

Diisopropylethylamine

INDABOX:

Bis(3a,8a-dihydro-8H-indeno[1,2d]oxazole

MS 4 Å:

4 Å Molecular sieves

MS:

Molecular sieves

Pybox:

2,6-Bis(oxazolinyl)pyridine

Rh2[(R)-DBBNP]4:

Dirhodium(II) tetrakis[(R)-6,6’-didodecylbinaphtholphosphate]

Rh2(S-BTPV)4:

Dirhodium(II) tetrakis[N-benzene-fused-phthaloyl-(S)-valinate]

Rh2[(S)-DOSP]4:

Dirhodium(II) tetrakis[(S)-N-(4-dodecylphenylsulfonyl)prolinate]

Rh2(S-PTTL)4:

Dirhodium(II) tetrakis[N-phthaloyl-(S)-tert-leucinate]

TADDOLα,α,α′,α′:

Tetraaryl-1,3-dioxolan-4,5-dimethanole

Tox:

Trisoxazoline

XABOX:

Bis(2-oxazolinyl)xanthene

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Ackowledgments

I wish to thank my coworkers, whose names appear on the cited papers. Financial support for this work by a Grant-in Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan is gratefully ackowledged.

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Authors and Affiliations

  1. Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano, 380-8553, Japan

    Hiroyuki Suga

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Correspondence to Hiroyuki Suga .

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Editors and Affiliations

  1. Faculty of Pharmaceutical Sciences, Chiba Institute of Science, Shiomi-Cho 15-8, Chiba, 288-0025, Japan

    Kiyoshi Matsumoto

  2. Graduate School of Science &, University of Toyama, Gofuku 3190, Toyama, 930-8555, Japan

    Naoto Hayashi

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Suga, H. (2009). Asymmetric 1,3-Dipolar Cycloaddition Reactions Catalyzed by Heterocycle-Based Metal Complexes. In: Matsumoto, K., Hayashi, N. (eds) Heterocyclic Supramolecules II. Topics in Heterocyclic Chemistry, vol 18. Springer, Berlin, Heidelberg. https://doi.org/10.1007/7081_2009_1

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