The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects

Maryanoff, Bruce E.; Reitz, Allen B.

doi:10.1021/cr00094a007

Cited by 2,500 publications

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“…Several excellent reviews on the topic have previously been written that contain extensive detail on the Wittig reaction mechanism. 2,3,4,5 M ore recent reviews do 25 not focus on the details of the mechanism. 6,7,8 The reaction (see Scheme 1) occurs between a carbonyl compound (aldehyde or ketone in general, 2) and a phosphonium ylide (1) to give alkene (3) with phosphine oxide (4) as the by-product.…”

Section: Recent Developmentsmentioning

confidence: 99%

The modern interpretation of the Wittig reaction mechanism

2013

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Section: Recent Developmentsmentioning

confidence: 99%

The modern interpretation of the Wittig reaction mechanism

2013

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“…Several approaches have been developed for generating acyclic trisubstituted alkenes, but these have key shortcomings. Unless an α-alkoxy ketone is involved 6 , Wittig-type transformations are minimally stereoselective 7,8 . Protocols for converting alkynes or carbonyl-containing compounds to trisubstituted alkenes entail lengthy sequences 9,10,11 , strongly acidic or basic conditions 10,11,12,13 , and/or just one stereoisomer 12,14 can be accessed (see the Supplementary Information, Section 1, for extended bibliography).…”

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Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

Nguyen

Koh

Mann

et al. 2017

Nature

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Catalytic cross-metathesis is a central transformation in chemistry, and yet, corresponding methods for stereoselectively generating acyclic trisubstituted alkenes in either isomeric form do not exist. The key problems are lack of chemoselectivity, namely, the preponderance of side reactions involving only the less hindered starting alkene, ensuing nonproductive processes of homo-metathesis byproducts, and formation of short-lived methylidene complexes. In contrast, in catalytic cross-coupling, another widely used process, substrates are more distinct and homocoupling is less of a problem. Here, we show that through cross-metathesis reactions involving E- or a Z-trisubstituted alkenes, easily prepared from commercially available starting materials by cross-coupling processes, many otherwise desirable and difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to >98% E or 95% Z). Utility is highlighted through concise stereoselective syntheses of biologically active compounds such as indiacen B (anti-fungal) and coibacin D (anti-inflammatory).

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“…In a typical Wittig reaction, carbonyl compounds are treated with phosphorus ylides to give the corresponding alkenes and phosphane oxide. [2] Sometimes, however, the 21 carbonyl compound is not readily available and has to be prepared by oxidation of the precursor alcohol. In fact, the oxidation of primary alcohols to aldehydes and subsequent Wittig reaction is a common practice in organic synthesis.…”

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Wittig‐Type Olefination of Alcohols Promoted by Nickel Nanoparticles: Synthesis of Polymethoxylated and Polyhydroxylated Stilbenes

2009

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Nickel nanoparticles were found to promote the Wittig‐type olefination of primary alcohols with phosphorus ylides. The latter can be prepared from the corresponding phosphonium salts with nBuLi or in situ generated with lithium metal. The methodology is especially efficient for the synthesis of stilbenes and is applied in the absence of any additive as ahydrogen acceptor. A new approach to the synthesis of polymethoxylated and polyhydroxylated stilbenes, including resveratrol, DMU‐212 and analogues, is presented.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects

Cited by 2,500 publications

References 0 publications

The modern interpretation of the Wittig reaction mechanism

The modern interpretation of the Wittig reaction mechanism

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

Wittig‐Type Olefination of Alcohols Promoted by Nickel Nanoparticles: Synthesis of Polymethoxylated and Polyhydroxylated Stilbenes

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