83126-02-7Relevant academic research and scientific papers
Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols
Larionov, Evgeny,Lin, Luqing,Gune, Laure,Mazet, Clment
supporting information, p. 16882 - 16894 (2015/01/09)
Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.
Stereochemically controlled Synthesis of Unsaturated Alcohols by the Horner-Wittig Reaction
Ayrey, Peter M.,Bolton, Michael A.,Buss, Antony D.,Greeves, Nicholas,Levin, Daniel,et al.
, p. 3407 - 3418 (2007/10/02)
Single isomers (E or Z) of unsaturated alcohols with two to five carbon atoms between the double bond and the OH group may be made by the phosphine oxide version of the Horner-Wittig reaction.Hydroxyalkyldiphenylphosphine oxides react with aldehydes either directly or as silyl ethers to give a moderately Z-selective synthesis, while rearrangement of esters of the same alcohols by acyl transfer or acylation of alkyldiphenylphosphine oxides with lactones gives hydroxy ketones whose reduction and elimination leads to an E-selective synthesis.In most cases, separation of the diastereoisomers of the Horner-Wittig intermediates leads to the preparation of pure E- or Z-alkenols.
ACYL TRANSFER REACTIONS WITH PHOSPHINE OXIDES: SYNTHESIS OF E-HOMOALLYLIC ALCOHOLS, CYCLOPROPYL KETONES, AND γ-HYDROXY KETONES
Wallace, Paul,Warren, Stuart
, p. 2971 - 2978 (2007/10/02)
Esters of 3-hydroxypropylphosphine oxides rearrange in base by O to C acyl (RCO) transfer to give the hydroxy ketones (8). threo-Selective reduction of (8) leads to pure E-homoallylic alcohols whilst C to O acyl )Ph2PO) transfer leads to γ-hydroxy ketones with nucleophilic aqueous base or cyclopropyl ketones with BuOKt - HOBut.
SYNTHESIS OF E-HOMOALLYLIC ALCOHOLS, γ-HYDROXYKETONES, AND CYCLOPROPYL KETONES FROM 3-DIPHENYLPHOSPHINOYL (Ph2PO) PROPANOLS BY ACYL TRANSFER
Wallace, Paul,Warren, Stuart
, p. 5713 - 5716 (2007/10/02)
Carboxyl transfer (O*C) on 3-Ph2PO propyl esters (9) gives an intermediate (10) from which the Ph2PO group may be removed by the Horner-Witting reaction or by Ph2PO transfer (C*O) to give the title compounds.
SYNTHESIS OF SINGLE ISOMERS (E OR Z) OF UNSATURATED ALCOHOLS BY THE HORNER-WITTIG REACTION
Buss, Antony D,Greeves, Nicholas,Levin, Daniel,Wallace, Paul,Warren, Stuart
, p. 357 - 360 (2007/10/02)
Single isomers (E or Z) of homoallylic and higher alcohols can be synthesised from ω-hydroxyalkyldiphenylphosphine oxides and aldehydes, or from alkyldiphenylphosphine oxides and lactones
Reactivity of 1-Cyclopropene-1-carboxylic Acid Lactones Dependent on the Size of the Lactone Ring
Frenking, Gernot,Huelskaemper, Ludwig,Weyerstahl, Peter
, p. 2826 - 2835 (2007/10/02)
The reaction of the bicyclic γ-lactone 1 with KOtBu leads to lactone 3 by addition of tert-butoxide at the 1-position of the intermediate cyclopropene lactone 2 and subsequent exo-protonation.In contrast, the δ-lactone 13, readily available from cinnamyl
