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Review
. 2009 Nov;38(11):3193-207.
doi: 10.1039/b821092f. Epub 2009 Sep 23.

Total synthesis of chiral biaryl natural products by asymmetric biaryl coupling

Marisa C Kozlowski  1 , Barbara J Morgan, Elizabeth C Linton
Affiliations
Review

Total synthesis of chiral biaryl natural products by asymmetric biaryl coupling

Marisa C Kozlowski et al. Chem Soc Rev. 2009 Nov.

Abstract

This tutorial review highlights the use of catalytic asymmetric 2-naphthol couplings in total synthesis. The types of chirality, chiral biaryl natural products, prior approaches to chiral biaryl natural products, and other catalytic asymmetric biaryl couplings are outlined. The three main categories of chiral catalysts for 2-naphthol coupling (Cu, V, Fe) are described with discussion of their limitations and advantages. Applications of the copper catalyzed couplings in biomimetic syntheses are discussed including nigerone, hypocrellin, calphostin D, phleichrome, and cercosporin.

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Figures

Figure 1
Figure 1
Types of Stereounits
Figure 2
Figure 2
Biaryls in Nature
Scheme 1
Scheme 1
Synthesis of Gossypol
Scheme 2
Scheme 2
Synthesis of Knipholone
Scheme 3
Scheme 3
Asymmetric Couplings with Aryl Halides
Scheme 4
Scheme 4
Asymmetric Copper Mediated Naphthol Coupling
Scheme 5
Scheme 5
Copper Catalyzed Asymmetric Homocoupling in the Presence of a Prolyldiamine
Scheme 6
Scheme 6
Sequential Mechanism for Copper Catalyzed Asymmetric Biaryl Coupling
Scheme 7
Scheme 7
Copper catalyzed Asymmetric Homo-coupling in the Presence of an H8-BINAM
Scheme 8
Scheme 8
Asymmetric Homocoupling Catalyzed by a Copper-salen Complex
Figure 3
Figure 3
Vanadium-Derived Catalysts
Scheme 9
Scheme 9
Asymmetric Homocoupling Under Electrochemical Conditions
Scheme 10
Scheme 10
Ruthenium- and Iron-catalyzed Asymmetric Couplings of 2-Naphthols
Figure 4
Figure 4
Retron for the Erythrina Alkaloid Family
Figure 5
Figure 5
Phenolic Coupling Retron for the Morphine Alkaloid Family
Scheme 11
Scheme 11
Enzymatic and Cell Culture Catalyzed Asymmetric Naphthol Couplings
Scheme 12
Scheme 12
Construction of Functionalized 2-Naphthols
Scheme 13
Scheme 13
Further Functionalization of 7-Halo-2-Naphthols
Scheme 14
Scheme 14
Retrosynthetic Analysis of Nigerone
Figure 6
Figure 6
Effect of Substitution Patterns on Enantioselectivity
Scheme 15
Scheme 15
Total Synthesis of Nigerone
Scheme 16
Scheme 16
Mechanism of Eight-Step Base Isomerization
Figure 7
Figure 7
Calculated and Experimental CD Spectra
Figure 8
Figure 8
Perylenequinone Natural Products
Figure 9
Figure 9
Atropisomerization of the Helical Perylene Core
Scheme 17
Scheme 17
Diastereomeric Biaryl Couplings Toward the Calphostins.
Scheme 18
Scheme 18
Retrosynthetic Considerations Toward the Perylenequinones
Scheme 19
Scheme 19
Common Enantiopure Intermediate 32i
Scheme 20
Scheme 20
Highly Functionalized Biaryl Coupling of Iodonaphthol 87
Scheme 21
Scheme 21
Dynamic Stereochemistry Transfer
Scheme 22
Scheme 22
Total Synthesis of Hypocrellin A
Figure 10
Figure 10
Common Enantiopure Intermediate to Perylenequinones
Scheme 23
Scheme 23
Biaryl Coupling of Iodonaphthol in the Total Syntheses of ent-Phleichrome and ent-Calphostin D
Scheme 24
Scheme 24
Synthetic Considerations for Cercosporin
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References

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