Unusual 1,2-migration in organoaluminiun chemistry, promoted by BF3.OEt2.

Alexakis, A.; Hanaizi, Jezia; Jachiet, D.; Normant, Jean F.; Toupet, Loı̈c

doi:10.1016/s0040-4039(00)88783-3

Cited by 27 publications

(5 citation statements)

References 9 publications

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“…In the dihydrofuran series, ringopening byproducts form (Table 88). 459 Hevesi and co-workers published in 1999 a similar electrophile-initiated rearrangement from 1-alkynylaluminum ate complexes (Table 89). 460 Taniguchi et al showed in 1991 that 1,2-migration with alkyl transfer can take place from a tetracoordinate Al to an adjacent carbon bearing an oxygen atom, with epoxide opening followed by syn-elimination to generate olefins (Table 90).…”

Section: Reactions Of Nu-homomaasmentioning

confidence: 92%

“…The products are obtained through 1,2-migration of a substituent from Al to the α-carbon, with concomitant grafting of the electrophile to the β-carbon. In the dihydrofuran series, ring-opening byproducts form (Table ) . Hevesi and co-workers published in 1999 a similar electrophile-initiated rearrangement from 1-alkynylaluminum ate complexes (Table ) .…”

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

confidence: 97%

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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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Section: Reactions Of Nu-homomaasmentioning

confidence: 92%

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

confidence: 97%

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

2013

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“…Interestingly, it has been proposed that the above dyotropic rearrangement is not restricted to Cu-compounds but also to boron, 163 zinc, 164 zirconium, 165 or aluminum. 166 However, there are few mechanistic details available and no firm evidence to suggest that all metallates abide by the same formal type I dyotropic mechanism. 156…”

Section: Applications Of the Dyotropic Rearrangement Of 5-lithiodihyd...mentioning

confidence: 99%

Dyotropic Reactions: Mechanisms and Synthetic Applications

2009

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Israel Ferna ´ndez (Madrid, 1977) enjoyed studying chemistry at the Universidad Complutense of Madrid (UCM). In 2005, he earned his Ph.D. in Chemistry at the UCM under the supervision of Prof. Miguel A. Sierra and received the Prize for the best Doctoral Thesis in Synthetic Chemistry by the Spanish Royal Society of Chemistry and the Lilly-Young Researcher Prize. After that, he joined the Theoretical and Computational Chemistry group of Prof. G. Frenking at the Philipps Universita ¨t Marburg as a postdoctoral researcher studying the bonding situation and reaction mechanisms of organic and organometallic compounds. At the present, I.F. is a Ramo ´n y Cajal fellow at the UCM. His current research includes the computational study of the bonding situation and reaction mechanisms of organic, organometallic, and bioorganic compounds with special interest in C-C bond forming processes.

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“…Treating Li-DHP with a triorganoaluminium reagent at Ϫ78 to Ϫ20 ЊC generates an intermediate aluminate species 313. 274 In the absence of BF 3 ؒOEt 2 , no reaction occurs with added electrophiles such as benzaldehyde or cyclohexene oxide. However, in the presence of stoichiometric BF 3 ؒOEt 2 , a novel 1,2-migration followed by nucleophilic attack on the electrophile produces the substituted DHP derivatives 314 and 315 (Scheme 88).…”

Section: Transmetalationmentioning

confidence: 99%

Generation and reactivity of α-metalated vinyl ethers

Friesen

2001

J. Chem. Soc., Perkin Trans. 1

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Unusual 1,2-migration in organoaluminiun chemistry, promoted by BF3.OEt2.

Cited by 27 publications

References 9 publications

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

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

Dyotropic Reactions: Mechanisms and Synthetic Applications

Generation and reactivity of α-metalated vinyl ethers

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