Preparation of new chiral building blocks via asymmetric catalysis

Iwamoto, Mitsuhiro; Kawada, Hatsuo; Tanaka, Tomoyuki; Nakada, Masahisa

doi:10.1016/j.tetlet.2003.08.009

Cited by 30 publications

(19 citation statements)

References 15 publications

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“…This chemistry has already been comprehensively reviewed elsewhere, 64 and therefore, is not discussed here. Nonetheless, some influential examples of biocatalytic desymmetrisations of 30 compounds with pro-stereogenic carbons (cyclopentane-1,3diones 60, 65 cyclohexane-1,3-diones 62, 66 bicyclic diketones 64, 67 and acyclic diketones 66 68 The outstanding method from Yamada and co-workers in desymmetrising acyclic 1,3-diketones by catalytic borohydride reduction in the presence of a chiral -ketoiminato cobalt(II) 45 catalyst furnished the corresponding aldol-type compounds 72 with high diastereoselectivity (de > 98% in favour of the anti diastereoisomer) and enantioselectivity (up to 99% ee; see Scheme 6 (a)). Yamada's method 69 is an interesting alternative to aldol-chemistry for the preparation of highly enantioenriched hydroxyketones, with the inherent attractiveness that the stereoselective preparation of enolates is not required.…”

Section: Methodsmentioning

confidence: 99%

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

et al. 2013

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Herein an overview of reductive catalytic enantioselective desymmetrisation of achiral or meso compounds is provided. The most efficient reductive desymmetrisations described in the literature, which involve the reduction of C=O, C=N, C=C and C-halogen bonds, or reductive ring-opening, are summarised. The structural diversity of the valuable highly enantioenriched intermediates prepared by reductive desymmetrisation is highlighted.

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Section: Methodsmentioning

confidence: 99%

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

et al. 2013

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“…We envisaged that 2 could be prepared from diketone 3 via intramolecular aldol reaction, followed by dehydration, installation of the isopropyl group, and dehydration. Diketone 3 was disconnected to give the two chiral fragments 4 and 5 , which could be prepared from novel chiral building blocks previously reported by us, i.e., by CAIMCP[17] and baker's yeast reduction,[18a,b] respectively.…”

Section: Total Synthesis Of (+)‐Allocyathin B2[14a]mentioning

confidence: 99%

Enantioselective Total Syntheses of Cyathane Diterpenoids

Nakada

2014

The Chemical Record

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A Personal Account describing the enantioselective total syntheses of cyathane diterpenoids achieved in the Nakada group. A convergent approach to the cyathane scaffold, the [5-6-7] tricyclic carbon skeleton commonly found in cyathane diterpenoids, has been developed using the catalytic asymmetric intramolecular cyclopropanation (CAIMCP) and baker's yeast reduction. This approach has been successfully applied for the enantioselective total syntheses of (+)-allocyathin B2 , (-)-erinacine B, and (-)-erinacine E. The total synthesis of (-)-erinacine E has been achieved via the acyl group migratory intramolecular aldol reaction, which prevents the retro-aldol reaction and allows the construction of the strained structure. The highly efficient and stereoselective total syntheses of (-)-scabronines G, A, D, and (-)-episcabronine A have been achieved via the oxidative dearomatization/inverse electron demand Diels-Alder reaction cascade. Cascade reactions comprising three and five consecutive reactions were employed for the highly efficient total syntheses of (-)-scabronine A and (-)-episcabronine A, respectively.

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“…In order to target this cyathane diterpenoid molecule, Nakada envisioned a convergent strategy starting with aldehyde 90 and alkyl iodide 91 (Scheme 23). Both fragment 90 and fragment 91 were prepared in enantioenriched form based on previous work published by Nakada and coworkers 34,35. After lithiumhalogen exchange was performed on iodide 91 , the resulting alkyl lithium was added to a solution of aldehyde 90 to provide access to alcohol 92 .…”

Section: Cyathane Total Synthesesmentioning

confidence: 99%

Synthetic efforts toward cyathane diterpenoid natural products

Enquist

Stoltz

2009

Nat. Prod. Rep.

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An overview of synthetic efforts toward cyathane diterpenoid natural products from the year 2000 to present is provided. The emphasis of this review is the various ring-constructing and stereoforming strategies employed in these synthetic routes. 1 Introduction 2 Overview of the cyathane diterpenoids 2.1 Isolation 2.2 Bioactivity 2.3 Biosynthesis 3 Strategy summary 4 Cyathane core syntheses 4.1 Wender's cyathane core synthesis 4.2 Desma€ ele's cyathane core synthesis 4.3 Takeda's cyathane core synthesis 5Cyathane total syntheses 5.1 Snider's (AE)-allocyathin B 2 and (+)-erinacine A 5.2 Tori's (AE)-allocyathin B 2 5.3 Piers' (AE)-sarcodonin G 5.4 Ward's (AE)-allocyathin B 3 5.5 Ward's (À)-cyathin A 3 5.6 Nakada's (+)-allocyathin B 2 5.7 Nakada's (À)-erinacine B 5.8 Nakada's (À)-erinacine E 5.9 Trost's (+)-allocyathin B 2 5.10 Danishefsky's (À)-scabronine G 5.11 Phillip's (+)-cyanthiwigin U, (+)-cyanthiwigin W, and (À)-cyanthiwigin Z 5.12 Reddy's (+)-cyanthiwigin AC 5.13 Stoltz's (À)-cyanthiwigin F 6 Conclusions 7 Acknowledgements 8 References

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Preparation of new chiral building blocks via asymmetric catalysis

Cited by 30 publications

References 15 publications

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

Catalytic enantioselective reductive desymmetrisation of achiral and meso compounds

Enantioselective Total Syntheses of Cyathane Diterpenoids

Synthetic efforts toward cyathane diterpenoid natural products

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