Notes. Metalation of Cyclopropane by Amylsodium

Lanpher, Edward J.; Redman, L. V.; Morton, Avery A.

doi:10.1021/jo01103a601

Cited by 15 publications

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“…The abstraction of protons from sp 3 centers using Na,Na bases is difficult but possible, as exemplified by cyclopropane employing PentNa 3 i-PrONa. 687 The same authors observed that the meta to para ratio of the PentNa-mediated dimetalation of benzene depends on the metal of ROM (R = alkyl, M = metal) employed to activate the organometal reagent, with the proportion of meta decreasing in the order Li > Na > K. In addition, the dimetalation is more favored in the presence of Na or K alkoxides than in the presence of Li alkoxides. Other substrates than benzene are similarly dimetalated at 60 °C: thiophene at its 2,5-positions, tert-butylphenoxide at its 2,6-positions, and isopropylbenzene and secbutylbenzene at their 3,5-positions.…”

Section: Reactions Of Maas Involving Base Ligand Transfer Processes (...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 Maas Involving Base Ligand Transfer Processes (...mentioning

confidence: 97%

“…The latter is able to metalate benzene (12 days, 11% yield), 1-hexene (12 days, 42%), toluene (8 days, 53%), and fluorene (7 days, 88%). The abstraction of protons from sp 3 centers using Na,Na bases is difficult but possible, as exemplified by cyclopropane employing PentNa· i -PrONa …”

Section: Reactions Of Maas Involving Base Ligand Transfer Processes (...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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“…The oletinic hydrogen in 2,3,3-triniethyl-I -cyclopropene [64] is nearly as active as the hydrogen in acetylene; hence, it is replaced even with methyl-lithium. Cyclopropane [65] reportedly reacts with amylsodium to give cyclopropylsodium [66].…”

Section: C) Olefinsmentioning

confidence: 99%