The Reaction of (Trialkylsilyl)vinylketenes with Carbenoid Reagents:  A New [4+1] Annulation Route to Cyclopentenones

Loebach, Jennifer L.; Bennett, Dawn M.; Danheiser, Rick

doi:10.1021/ja982101r

Cited by 87 publications

(34 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[11,22] Oxyallyl is usually considered as the intermediate in allene oxide annulations [10,18,[23][24][25][26][27] or [4+1] annulations of vinyl ketenes. [28,29] The direct conversion of vinyl cyclopropanones to cyclopentenones by a sigmatropic [1,3] shift is also considered as a likely alternative. [28][29][30] Nevertheless, the formations of cyclopropanone 6 and 12-oxo-PDA are closely related, as both share the oxyallyl intermediate (5 b, Scheme 1).…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Novel Allene Oxide Synthase Products Formed via Favorskii‐Type Rearrangement: Mechanistic Implications for 12‐Oxo‐10,15‐phytodienoic Acid Biosynthesis

et al. 2011

View full text Add to dashboard Cite

The allene oxide synthase (AOS) pathway is widespread in plants. Its products, such as cyclopentenone 12-oxo-10,15-phytodienoic acid (12-oxo-PDA) and related jasmonates, play important biological roles in plants. We found that 12-oxo-PDA in some plant tissues co-occur with an unknown minor oxylipin 1. In vitro incubations of AOSs with α-linolenic acid 13(S)-hydroperoxide reliably afforded 1 along with 12-oxo-PDA and α-ketol. A similar oxylipin 3 was formed during the AOS conversions of γ-linolenic acid 9(S)-hydroperoxide. Linoleic acid hydroperoxides formed neither products similar to 1 and 3 nor cyclopentenones. Oxylipins 1 and 3 were purified and identified as the products of Favorskii-type rearrangement, (2'Z,4Z)-2-(2'-pentenyl)-4-tridecene-1,13-dioic acid and (2'Z,4Z)-2-(2'-octenyl)-4-decene-1,10-dioic acid, respectively. Detection of Favorskii products 1 and 3 demonstrates that cyclopropanones are short-lived AOS products along with allene oxides. The observed parallels between the Favorskii product 1 and 12-oxo-PDA formation suggests that cyclopropanone is either a byproduct or a precursor of 12-oxo-PDA.

show abstract

Section: Discussionmentioning

confidence: 99%

“…[28,29] The direct conversion of vinyl cyclopropanones to cyclopentenones by a sigmatropic [1,3] shift is also considered as a likely alternative. [28][29][30] Nevertheless, the formations of cyclopropanone 6 and 12-oxo-PDA are closely related, as both share the oxyallyl intermediate (5 b, Scheme 1).…”

Section: Discussionmentioning

confidence: 99%

Novel Allene Oxide Synthase Products Formed via Favorskii‐Type Rearrangement: Mechanistic Implications for 12‐Oxo‐10,15‐phytodienoic Acid Biosynthesis

et al. 2011

View full text Add to dashboard Cite

show abstract

“…[284] (Alkenyl)(silyl)ketenes 341, X ϭ SiR 3 , generated by Wolff rearrangement of 340, were found to accept diazomethanes in a novel [4 ϩ 1] annulation, with formation of cyclopentenones 366 (Scheme 47). [285] Electron-withdrawing groups [X ϭ P(O)(OMe) 2 , SO 2 Ph], on the other hand, lead to the formation of alkenes 367, presumably by way of cyclopropanones. [286] An analogous intramolecular reaction of bis(diazo)diketones produced cyclic enones, as exemplified by the conversion of 368 into 369, and of 370 into 371, preferably by thermolysis.…”

Section: Reactions With Diazo Compounds and Carbenesmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

View full text Add to dashboard Cite

The conversion of α‐diazo ketones into ketenes, and products derived therefrom, was discovered by Wolff in 1902. Major applications of the Wolff rearrangement, such as the Arndt−Eistert reaction (homologation of carboxylic acids) and the ring contraction of cyclic ketones, have been with us for some while. Nevertheless, substantial progress has been made recently. The reaction mechanism has been explored by means of matrix isolation, time‐resolved spectroscopy, and computation. Full retention of configuration of the migrating group has been established by using enantioselective chromatography. The Arndt−Eistert reaction has witnessed a renaissance in the field of natural products, in particular β‐amino acids and β‐peptides. Ring‐contracting Wolff rearrangements and ketene cycloadditions have been applied in syntheses of increasingly complex, biologically active target molecules. These accomplishments, as well as unsolved problems, are addressed in the present review. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

show abstract

“…As a consequence, sulfur ylides are widely utilized for the construction of epoxide, aziridine, and cyclopropane architectures. Recently, studies by Tang and co-workers [7] and others [8] have significantly extended the scope of the ylide-initiated reactions and outlined the first examples of tandem reactions initiated by sulfur ylides to furnish a range of functionalized cyclic compounds beyond three-membered rings. Despite the advances, the search for unprecedented ylide-based multiple cascade reactions continues, with the goal of increasing the diversity of possible substrates and the architectural complexity of products in a step-economical fashion.…”

mentioning

confidence: 99%

Construction of Fused Heterocyclic Architectures by Formal [4+1]/[3+2] Cycloaddition Cascade of Sulfur Ylides and Nitroolefins

et al. 2009

Angew Chem Int Ed

View full text Add to dashboard Cite

Over the last 50 years, seminal research from the groups of Franzen, [1] Corey, [2] Trost, [3] Aggarwal, [4] and Dai [5] have established sulfur ylides [6] as valuable and versatile intermediates in synthetic chemistry. As a consequence, sulfur ylides are widely utilized for the construction of epoxide, aziridine, and cyclopropane architectures. Recently, studies by Tang and co-workers [7] and others [8] have significantly extended the scope of the ylide-initiated reactions and outlined the first examples of tandem reactions initiated by sulfur ylides to furnish a range of functionalized cyclic compounds beyond three-membered rings. Despite the advances, the search for unprecedented ylide-based multiple cascade reactions continues, with the goal of increasing the diversity of possible substrates and the architectural complexity of products in a step-economical fashion.[9] Recently, our laboratory implemented a new reaction of sulfur ylides with nitroolefins to afford diverse and structurally complex oxazolidin-2-ones, wherein a transiently generated cyclic nitronate was involved.[10] On this basis, we became interested in the possibility of using the above mentioned cyclic nitronate as a suitable 1,3-dipole to react with electron-deficient components in situ, and in doing so create multiple bonds, rings, and stereocenters in a single transformation. Herein, we report a successful execution of this idea and describe the first intermolecular [4+1]/intramolecular [3+2] cycloaddition cascade of sulfur ylides and alkene-tethered nitroolefins.[11] This novel and catalyst-free strategy allows rapid access to functionalized 2,3,5-trioxa-2a-azapentaleno[1,6-ab]naphthalenes, 2,3-dioxa-5-thia-2a-azapentaleno[1,6-ab]naphthalenes, and isoxazolo[4,3,2-hi][2,1]benzisoxazoles in a highly concise fashion (Scheme 1); and these products are versatile synthons for the construction of densely functionalized chromans, thiochromans, amino acids, amino alcohols, and other important heterocycles. [12] We initially studied the reaction of dimethyl (2-oxo-2-phenylethyl)sulfonium ylide (1 a) with (E)-ethyl 3-(2-((E)-2-nitrovinyl)phenoxy)acrylate (2 a) in acetonitrile at 0 8C for 12 hours, at which point the reaction mixture was warmed to room temperature and stirred for an additional eight hours. To our delight, the proposed cycloaddition cascade was indeed facile and afforded ethyl 1-(phenylcarbonyl)-4,4a,9b,9c-tetrahydro-1H-2,3,5-trioxa-2a-azapent-aleno[1,6-ab]naphthalene-4-carboxylate (4 a) as a major isolable product in 43 % yield with great diastereocontrol (Table 1, d.r.[c]

show abstract

The Reaction of (Trialkylsilyl)vinylketenes with Carbenoid Reagents: A New [4+1] Annulation Route to Cyclopentenones

Cited by 87 publications

References 17 publications

Novel Allene Oxide Synthase Products Formed via Favorskii‐Type Rearrangement: Mechanistic Implications for 12‐Oxo‐10,15‐phytodienoic Acid Biosynthesis

Novel Allene Oxide Synthase Products Formed via Favorskii‐Type Rearrangement: Mechanistic Implications for 12‐Oxo‐10,15‐phytodienoic Acid Biosynthesis

100 Years of the Wolff Rearrangement

Construction of Fused Heterocyclic Architectures by Formal [4+1]/[3+2] Cycloaddition Cascade of Sulfur Ylides and Nitroolefins

Contact Info

Product

Resources

About