- A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
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Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
- Guin, Joyram,Paul, Subhasis
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supporting information
p. 4412 - 4419
(2021/02/05)
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- CROSS-COUPLIN REACTIONS BETWEEN SOME ALLYL, HOMOALLYL, AND HOMOPROPARGYL SUBSTRATES AND TRIALKYLALANES OR DIALKYL- AND DIARYL-MAGNESIUM DERIVATIVES
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Trialkylalanes and dilkyl- and diaryl-magnesium derivatives can be cross-coupled with allyl ethers and esters, sulphides, and quaternized allylamines.The reactions proceed uncatalyzed either with mild conditions or in the presence of copper complex catalysts to result in high yields of mono- and di-olefins of various structures.The alkylation of homoallyl or homopropargyl tosylates by trialkylalanes is accompanied by cyclization, which leads to alkyl-substituted cyclopropanes. i.e. cyclobutanes and cyclopropylidenes.
- Tolstikov, G. A.,Dzhemilev, U. M.
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p. 133 - 144
(2007/10/02)
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- THE EFFECT OF CROWN ETHER ON STERIC HINDRANCE TO BASE APPROACH IN BIMOLECULAR ELIMINATION: EVIDENCE AGAINST CLUMP AGGREGATE MODEL OF ION-PAIRED ALKOXIDE BASE
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The effect of 18-crown-6-ether upon geometrical orientation and rates was investigated in tert-C4H9OK-tert-C4H9OH promoted anti-elimination from two homologous series of tosylates, RCH2CHOTsC5H11 and RCHOTsCH2C5H11 (R = H, CH3, C2H5, n-C3H5, iso-C3H7, tert-C4H9).Steric requirements of the cis- and trans-stereoselective base species operating in the reaction in the absence and in the presence of the crown ether, respectively, have been assessed.An unambiguous distinction has been made between two pending models of the cis-stereoselective (ion-paired) base.
- Pankova, Magdalena,Zavada, Jiri
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p. 3150 - 3159
(2007/10/02)
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