New synthesis of aldehydes via vinylsilanes

Stork, Gilbert; Colvin, Ernest W.

doi:10.1021/ja00737a057

Cited by 139 publications

(25 citation statements)

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“…A) Stereoselective (cis + Z , fruns + E, ca. 95% ds) rearrangement of silyloxiranes to Si enol ethers [319,320]. B) Attack of an oxonium ion on a vinyl silane, leading to an oxepane via substitution with retention (R=Bu, R = H and R = H , R = B u , 98% ds) [321].…”

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confidence: 99%

Organic Synthesis—Where now?

Seebàch¹

1990

Angew. Chem. Int. Ed. Engl.

566

224

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This review article is an attempt to sketch the important developments in organic synthesis during the past 25 years, and to project them into the future.—The primary motivations that once induced chemists to undertake natural product syntheses no longer exist. Instead of target structures themselves, molecular function and activity now occupy center stage. Thus, inhibitors with an affinity for all the important natural enzymes and receptors have moved to the fore as potential synthetic targets.—New synthetic methods are most likely to be encountered in the fields of biological and organometallic chemistry. Enzymes, whole organisms, and cell cultures for enan‐tioselective synthesis of specific substances have already been incorporated into the synthetic arsenals of both research laboratories and industry. In addition, designing appropriate analogues to transition states and intermediates should soon make it possible, with the aid of the mammalian immune system and gene technology, to prepare catalytically active monoclonal antibodies for almost any reaction; perhaps, more important, such processes will increasingly come to be applied on an industrial scale.‐The discovery of truly new reactions is likely to be limited to the realm of transition‐metal organic chemistry, which will almost certainly provide us with additional “miracle reagents” in the years to come. As regards main group elements (“organoelemental chemistry”), we can surely anticipate further stepwise improvements in experimental procedures and the broader application of special techniques, leading to undreamed of efficiency and selectivity with respect to known procedures. The primary center of attention for all synthetic methods will continue to shift toward catalytic and enantioselective variants; indeed, it will not be long before such modifications will be available with every standard reaction for converting achiral educts into chiral products. Analysis, spectroscopy, structure determination, theory, and electronic data processing have all become indispensable in organic synthesis. Only with the aid of these “tools” will the methods of organic chemistry permit selective syntheses of ever larger and more complex systems on both the molecular and supramolecular levels.—Examples have been introduced throughout this discourse to illustrate its many themes, and a very comprehensive bibliography should help the interested reader become more familiar with important keywords and authors.[ ]—This article will have served its intended purpose if it changes the minds of some of those who claim organic chemistry is a mature science, and if it causes students to discover the vitality and forcefulness with which organic synthesis is meeting new challenges and attempting to fulfill old dreams. Er zeigt uns so in seinem wissenschaftlichen Leben, daß die Chemie nicht von einer Theorie, nicht von einer Methode aus zu erschöpfen ist, und daß Erkenntnis und Nutzen in ihr untrennbar verwoben sind. R. Koch, writing about Louis Pasteur

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confidence: 99%

Organic Synthesis—Where now?

Seebàch¹

1990

Angew. Chem. Int. Ed. Engl.

566

224

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“…45 2.5. a-Trimethylsilyl epoxides a-Trimethylsilyl epoxides were introduced by Stork et al 46 who showed that epoxidation of a vinylsilane gave an a-trimethylsilyl epoxide. Magnus et al 48 introduced the formation of a-trimethylsilyl epoxides by chemistry that was closely analogous to the classical Darzens reaction.…”

Section: A-ester Epoxidesmentioning

confidence: 99%

Homologation of ketones into carboxylic acids

Badham¹

2004

Tetrahedron

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“…[8] Vinylsilanes are well-known to be easily oxidized into α,β-epoxysilanes, which are useful intermediates for the preparation of carbonyl compounds. [9] It has also been shown that pure cis or trans α,β-epoxysilanes can be readily converted into heterosubstituted alkenes, such as vinyl halides, in high stereochemical purity. [10] Thus, the Z vinyl chloride 8 can be prepared in a simple way from vinylsilane 4e (E/ Z: 95:5) by oxidation, followed by treatment with HCl, in 59% overall yield (Scheme 3).…”

Section: Study Of the Carbometalationmentioning

confidence: 99%