Boron trifluoride assisted opening of epoxides by lithium alkenyl aluminate reagents

Alexakis, Alexandre; Jachiet, D.

doi:10.1016/s0040-4020(01)85130-9

Cited by 25 publications

(5 citation statements)

References 8 publications

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“…Diastereoselective Synthesis of Pentasubstituted Tetrahydropyrans. To study the formation of pentasubstituted tetrahydropyran derivatives, commercially available cyclohexene oxide was converted into trans -2-(1-hepten-1-yl)cyclohexanol ( 9 ) in high yield by a method of Alexakis and Jachiet (Scheme ) . Condensations of 9 with both benzaldehyde and hexanal were carried out under the same standard reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹

2001

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Polysubstituted tetrahydropyrans and thiacyclohexanes were synthesized in high yields with excellent diastereoselectivities via indium trichloride mediated cyclizations between homoallyl alcohols and mercaptans with aldehydes. In the case of tetrahydropyran products, the stereochemistry of the product was found to be directly correlated with the geometry of the homoallyl alcohols; whereas the cross-cyclization of aldehydes with trans-homoallyl alcohols generated (up-down-up) 2,3,4-trisubstituted tetrahydropyran products exclusively, the reaction of aldehydes with cis-homoallyl alcohols provided mainly (up-up-up) 2,3,4-trisubstituted products. When a trisubstituted homoallyl alcohol was used, its cross-cyclization with aldehydes generated (up-down-up-down-up) pentasubstituted tetrahydropyran derivatives with simultaneous controlling of five stereogenic centers. On the other hand, a cyclization-decyclization equilibrium was observed in the formation of thiacyclohexanes. The reaction of both cis- and trans-homoallyl mercaptans with aldehydes provided the same major diastereomers.

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Section: Resultsmentioning

confidence: 99%

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹

2001

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“…In the presence of BF 3 ·Et 2 O, ate compounds of ( E )-(RCHCH)Me( i -Bu) 2 AlLi-type readily transfer their alkenyl group to achieve the opening of epoxides and even of oxetane (Table ). Alkenyl and alkynyl aluminates obtained by reaction of the corresponding Li reagents with Me 3 Al behave similarly (Scheme ) . The method has been used in the synthesis of 6-nor-fluvirucinin B 1 (Scheme ), in the preparation of chiral building blocks having 1,3- syn -Me groups (Scheme ), and at the beginning of the syntheses of (−)-mycalamide A (Scheme ) and amphidinolide P (Scheme ) .…”

Section: Reactions Of Maas Involving Nucleophile Ligand Transfer Proc...mentioning

confidence: 99%

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

2013

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6. Conclusion 7706 Author Information 7706 Biographies 7707 Acknowledgment 7707 Abbreviations Used 7707 References 7708the corresponding allyl-and propargylchromium reagents that further react with a variety of electrophiles to afford the corresponding adducts in high yields. 102 Bu 6 CrLi 3 similarly behaves as a formal two-electron reductant with ketones and esters bearing a leaving group at the α-position to produce enolates that are intercepted with a variety of electrophiles with high selectivities (Table 8). 103 Such enolates are also capable of reacting with oxiranes to afford γand β-hydroxy esters, depending on the Lewis acid used as promoter. 2143.2.2. Two-Electron Transfers from M,Mn-HeteroMAAs (M = Li, MgX). In 1976, Cahiez et al. disclosed the possible reduction in THF of alkenyl bromides or iodides, as well as aryl chlorides or bromides, using i-PrMgCl in the presence of a catalytic amount of MnCl 2 . 215 The authors proposed the in situ formation of unstable i-Pr 3 MnMgCl and its decomposition by β-elimination to H 3 MnMgCl; reaction of the latter with the halide would then afford an unstable Mn(IV) intermediate, able Scheme 23 Scheme 24 Scheme 21 Scheme 22

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“… [137] Thus, butynol 385 underwent a selective reduction to Z ‐olefin, a Sharpless asymmetric epoxidation, and a tosylation. A regioselective ring‐opening of the less hindered side of epoxide 386 was achieved with AlMe 3 ⋅Li trimethylsilylacetylide ate complex, and BF 3 ⋅OEt 2 [151] furnished the desired addition product. Subsequent displacement of the tosylate yielded epoxide 387 .…”

Section: Total Synthesis Of Amphidinolide C and Fmentioning

confidence: 99%

Advances Toward Amphidinolides C, F and U: Isolations, Synthetic Studies and Total Syntheses

Ciss,

Seck,

Figadère

et al. 2024

Chemistry A European J

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Amphidinolides C, F, and U, including C2‐C4 analogs, are highly cytotoxic marine macrolides, mainly isolated from dinoflagellates of the genus Amphidinium. All these polyketides share a 75% or more similar structure, highlighted by a macrolactone ring, at least one trans‐2,5‐substituted‐THF motif and a characteristic polyenic side chain. From their isolation and absolute configurational assignment, the total synthesis of these marine macrolides represented an intense challenge to the organic synthesis community over the last 15 years, with around 14 research groups engaged in this inspiring task. In the first part of this review, we present the different approaches to the isolation and characterization of these natural products, including the most recent analogs, which may cast doubt on the biogenetic origin of these compounds. The various synthetic approaches to the total synthesis of C, F, and U amphidinolides are presented in a second part, focusing on key reactions and/or innovative strategies. The review concludes in a third section summarizing the successful approaches leading to the total synthesis of one of the members of this amphidinolide subfamily.

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Boron trifluoride assisted opening of epoxides by lithium alkenyl aluminate reagents

Cited by 25 publications

References 8 publications

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

Advances Toward Amphidinolides C, F and U: Isolations, Synthetic Studies and Total Syntheses

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Boron trifluoride assisted opening of epoxides by lithium alkenyl aluminate reagents

Cited by 25 publications

References 8 publications

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations1

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations1

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

Advances Toward Amphidinolides C, F and U: Isolations, Synthetic Studies and Total Syntheses

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Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹

Diastereoselective Synthesis of Polysubstituted Tetrahydropyrans and Thiacyclohexanes via Indium Trichloride Mediated Cyclizations¹