An Improved Convergent Strategy for the Synthesis of Oligoprenols

Yu, Xiongjie; Zhang, Hao; Xiong, Fei; Chen, Xu‐Xiang; Chen, Fen‐Er

doi:10.1002/hlca.200890211

Cited by 7 publications

(1 citation statement)

References 21 publications

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“…According to our approach, the most logical precursor of alliodorol 1e is compound 9e, which is easily preparable by oxidation of geraniol acetate (9b) [23]. Hence, the latter ester was treated with tert-butyl hydroperoxide in the presence of a catalytic amount of SeO 2 to afford, regioselectively, alcohol 9e contaminated with the corresponding aldehyde.…”

Section: Synthesis Of Hydroquinone Meroterpenoidsmentioning

confidence: 99%

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

Serra

Lissoni

2014

Natural Product Communications

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A new general synthetic approach to hydroquinone meroterpenoids is here described. The framework of the aforementioned natural compounds was built up through the Li 2 CuCl 4 catalysed cross coupling reaction of the 4-substituted-(E)-prenyl acetates 9 with 2,5-bis(benzyloxy)phenyl magnesium bromide 8 as a key step. The latter sp 3-sp 2 coupling affords the products in good chemical yields and in very high stereoisomeric purity. A further key step of the present synthetic method consists of the removal of the benzylic protecting groups by a very mild procedure based on the use of lithium naphthalenide. The latter reagent, in combination with aliphatic dialkylamines, is able to cleave all the benzylic protecting groups leaving unaffected the polyenic moieties. By these means, we devised a new synthesis of the natural hydroquinone geranylhydroquinone, farnesylhydroquinone, metachromin V and alliodorol. In addition, the marine meroterpenoid, (+)-(S)-metachromin V, was synthesized for the first time; its chemical structure was confirmed and its absolute configuration was unambiguously assigned.

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Section: Synthesis Of Hydroquinone Meroterpenoidsmentioning

confidence: 99%

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

Serra

Lissoni

2014

Natural Product Communications

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Synthesis of Cembranoid Analogues through Ring‐Closing Metathesis of Terpenoid Precursors: A Challenge Regarding Ring‐Size Selectivity

Heidt

Baro

Köhn

2015

Chemistry A European J

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A systematic study on ring-closing metathesis with Grubbs II catalyst to cembranoid macrocycles is described. Acyclic terpenoids with a functional group X in the homoallylic position relative to an RCM active terminus and substituents R, R(1) directly attached to the other terminal double bond were prepared from geraniol derived trienes and fragments that are based on bromoalkenes and dimethyl malonate. Such terpenoids were suitable precursors, despite the presence of competing double bonds in their framework. The size of R and R(1) is crucial for successful macrocyclization. Whereas small alkyl substituents at the double bond directed the RCM towards six-membered ring formation, cross metathesis leading to dimers dominated for bulkier alkyl groups. A similar result was obtained for precursors without functional group X. In the case of unsymmetrically substituted terpenoid precursor (R = Et, R(1) = Me) with homoallylic OTBS or OMe group, the RCM could be controlled towards formation of macrocyclic cembranoids, which were isolated with excellent E-selectivity. The role of the substituents was further studied by quantum chemical calculations of simplified model substrates. Based on these results a mechanistic rationale is proposed.

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A convergent stereocontrolled synthesis of [3‐¹⁴C]solanesol

Roe¹,

Oldfield²,

Geach³

et al. 2013

Labelled Comp Radiopharmac

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In this communication, we report the synthesis of ~5 mCi of [3-(14) C]solanesol (1) prepared from ethyl [3-(14) C]acetoacetate and (all-E)-octaprenyl bromide (2) in four steps, with a specific radioactivity of 19.83 mCi/mmol and with a chemical/stereochemical and radiochemical purity of ≥ 95%. (Figure ). Position 3 of the chain was selected for (14) C labelling because of the metabolic stability of this position. Unlabelled (all-E)-octaprenyl (18) (Scheme ) necessary for this work was prepared via a convergent iterative 'allyl-allyl' coupling approach of precursors easily derived from readily available inexpensive starting materials.(1)

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An Improved Convergent Strategy for the Synthesis of Oligoprenols

Cited by 7 publications

References 21 publications

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

Synthesis of Cembranoid Analogues through Ring‐Closing Metathesis of Terpenoid Precursors: A Challenge Regarding Ring‐Size Selectivity

A convergent stereocontrolled synthesis of [3‐¹⁴C]solanesol

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An Improved Convergent Strategy for the Synthesis of Oligoprenols

Cited by 7 publications

References 21 publications

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

A General Synthetic Approach to Hydroquinone Meroterpenoids: Stereoselective Synthesis of (+)-(S)-Metachromin V and Alliodorol

Synthesis of Cembranoid Analogues through Ring‐Closing Metathesis of Terpenoid Precursors: A Challenge Regarding Ring‐Size Selectivity

A convergent stereocontrolled synthesis of [3‐14C]solanesol

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A convergent stereocontrolled synthesis of [3‐¹⁴C]solanesol