.alpha.-Methoxyvinyllithium and related metalated enol ethers. Practical reagents for nucleophilic acylation

Baldwin, Jack E.; Hoefle, G.; Lever, O. W. Jun.

doi:10.1021/ja00829a064

Cited by 206 publications

(68 citation statements)

References 1 publication

(1 reference statement)

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“…1-Ethoxy-1-lithioethene 54 252 by treatment with t-butyllithium in pentane in the presence of the cosolvent TMEDA (equation 36). t-Butyllithium in tetrahydrofuran 255 or tetrahydropyran 256 as well as a mixture of potassium t-butoxide and butyllithium 257 also bring about the deprotonation of alkyl vinyl ethers. A series of lithiated vinyl ethers have been generated according to this or similar procedures 258 -279 .…”

Section: Scheme 10 Decreasing Stability Of Alkyl-and Alkoxyalkyllithmentioning

confidence: 99%

“…Thus, lithiated methyl vinyl ether 56 and ethyl vinyl ether 54, available by deprotonation with t-or n-butyllithium, readily react with aldehydes, ketones and alkyl halides. When the enol ether moiety of the adducts formed in this way is submitted to an acid hydrolysis, methyl ketones are obtained as shown in equations 72 396 and 73 255 . Thus, the lithiated ethers 56 and 54 function as an acetaldehyde d 1 synthon 177.…”

Section: Reactions Typical Of Carbanionsmentioning

confidence: 99%

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Lithium Carbenoids

Braun

2009

Patai's Chemistry of Functional Groups

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Section: Scheme 10 Decreasing Stability Of Alkyl-and Alkoxyalkyllithmentioning

confidence: 99%

Section: Reactions Typical Of Carbanionsmentioning

confidence: 99%

Lithium Carbenoids

Braun

2009

Patai's Chemistry of Functional Groups

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“…As seen in Scheme 34, the MOM group at C6 position could be participated in transacetalation, the C25-OH of the syn aldol product 233, formed in Scheme 33, was protected as the MOM ether followed by reductive removal of the chiral auxiliary by using LiBH 4 [107] to give the primary alcohol 261 in 86% overall yield. The Swern oxidation of 261 formed an aldehyde which was reacted with α-lithio ethyl vinyl ether [135] at -110 °C to give the C7-β-OH intermediate in ≥20:1 diastereoselectivity. Protection of the C7-β-OH as the PMB ether by treating with KHMDSEt 3 N-PMBBr, followed by acidic hydrolysis of the vinyl ether group afforded the methyl ketone 262 in 79% overall yield.…”

Section: Total Synthesis Of Formamicinmentioning

confidence: 99%

Structures and Total Syntheses of the Plecomacrolides

Dai

Guan²,

Jin

2005

CMC

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The plecomacrolides are a large family of natural products typically featured with a 16- or 18-membered macrolactone possessing two conjugated diene units and a hemiacetal side chain. The macrocycle skeleton is connected with the side chain through a three-carbon linker, forming a biologically important intramolecular hydrogen bonding network among the lactone/linker/hemiacetal structural motif. Many members of the plecomacrolides act as selective inhibitors of vacuolar H+-ATPases (V-ATPases) and they are considered to have the potential for treatment of postmenopausal osteoporosis. Significant progress has been achieved in recent years in the area of plecomacrolide total synthesis. These include the total synthesis of bafilomycin A1 by Evans, Toshima, Hanessian, and Roush, of bafilomycin V1 by Marshall, of hygrolidin by Hashimoto and Yonemitsu, of concanamycin F by Paterson and Toshima, and of formamicin by Roush. The synthetic strategies and key transformations used in the total synthesis are discussed.

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“…[31] Das so erzeugte 1-Ethoxy-1-lithioethen 7 a läût sich NMR-spektrokopisch charakterisieren, wobei auch hier die typische Tief-feldverschiebung des Carbenoid-Kohlenstoffatoms (d 212) zu beobachten ist. [32] Ferner eignen sich tert-Butyllithium in Tetrahydrofuran [33] oder Tetrahydropyran [34] sowie das Gemisch aus Kalium-tert-butoxid und Butyllithium [35] zur Deprotonierung von Alkenylalkylethern. Nach diesen oder ähnlichen Verfahren können eine Reihe a-lithiierter Vinylether, beispielsweise 2-Lithio-4,5-dihydrofuran 17, [32,36,37] 2-Lithio-5,6-dihydropyran 18 [32,38] und 2-Lithio-5,6-dihydro-1,4dioxin 19, [39,40] sowie das metallierte Carbamid 20 [41] erhalten werden.…”

Section: Introductionunclassified