Simmons-Smith Research Articles

ChemInform Abstract: Synthesis of Dibenzo[b,f]cycloprop[d]azepine Derivatives. Part 1. Introduction of a Cyclopropane Ring by the Use of Simmons‐Smith Reagent. Conformational Analysis of 1,1a,6,10b‐Tetrahydrodibenzo[b,f]cycloprop[d]azepine Derivatives.

Chemischer InformationsdienstVolume 8, Issue 15 Heterocyclic Compounds ChemInform Abstract: Synthesis of Dibenzo[b,f]cycloprop[d]azepine Derivatives. Part 1. Introduction of a Cyclopropane Ring by the Use of Simmons-Smith Reagent. Conformational Analysis of 1,1a,6,10b-Tetrahydrodibenzo[b,f]cycloprop[d]azepine Derivatives. K. KAWASHIMA, K. KAWASHIMASearch for more papers by this authorY. KAWANO, Y. KAWANOSearch for more papers by this authorE. MIZUTA, E. MIZUTASearch for more papers by this author K. KAWASHIMA, K. KAWASHIMASearch for more papers by this authorY. KAWANO, Y. KAWANOSearch for more papers by this authorE. MIZUTA, E. MIZUTASearch for more papers by this author First published: April 12, 1977 https://doi.org/10.1002/chin.197715253Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue15April 12, 1977 RelatedInformation

ChemInform Abstract: The Reaction of Enol Ethers with Simmons‐Smith Reagent. The Formation of Allylic Ethers.

AbstractDie Enoläther (I) reagieren mit Dijodmethan in Äther in Gegenwart eines Zink‐Kupfer‐Paares zu den Alkoxynorcaranen (III) und den Alkoxymethylencyclohexanen (IV).

Formation of dibenzo[b,f]azecines by the reaction of 1-halogenophenethyl-1H-2-benzazepines with dimsylsodium.

Treatment of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-7, 8-dimethoxy-2-methyl-1H-2-benzazepine (7a) with dimsylsodium afforded 5, 6, 7, 8, 13, 14-hexahydrotrans-13, 14-methano-2, 3, 10, 11-tetramethoxy-5-methyldibenzo [b, f] azecine (8) and its cisisomer (9). The structure of the former was confirmed by direct comparison with the authentic sample prepared by the Simmons-Smith reaction of the 13, 14-trans-5, 6, 7, 8-tetrahydrodibenzo [b, f] azecine (11). 5, 6, 7, 8, 13, 14-Hexahydro-11-hydroxy-cis-13, 14-methano-2, 3, 10-trimethoxy-5-methyldibenzo [b, f] azecine (15) was obtained by the reaction of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-8-hydroxy-7-methoxy-2-methyl-1H-2-benzazepine (7b) with dimsylsodium. The same reaction by the use of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-7-hydroxy-8-methoxy-2-methyl-1H-2-benzazepine (7e) afforded the 13-(methylsulfinyl) methyl-5H-dibenzo [b, g] azacycloundecine (16).

THE REACTION OF ENOL ETHERS WITH SIMMONS–SMITH REAGENT. THE FORMATION OF ALLYLIC ETHERS

Abstract The Simmons–Smith reaction of methyl and ethyl cyclohexenyl ethers has resulted in the formation of allylic ethers, in addition to expected cyclopropyl ethers. In one case the allylic ether was obtained as the major product of this reaction.

Reaction of the Simmons-Smith reagent with trimethylamine-borane

Reaction of the Simmons-Smith reagent with trimethylamine-borane

ChemInform Abstract: THE CYCLOPROPANATION OF SILYL ENOL ETHERS. A POWERFUL SYNTHETIC TOOL

AbstractDer Artikel befaßt sich mit verbesserten Simmons‐Smith‐Reaktionen, der Cyclopropanierung von Silylenolaten gesättigter Aldehyde und Ketone sowie der Synthese von Hydroxybicyclo(n,1,0)alkenen.

SYNTHESIS OF CYCLOPROPYL ESTERS FROM SILYL ENOL ETHERS

Abstract Cyclopropyl esters are conveniently prepared by direct addition of acid halides to the reaction mixture of Simmons–Smith reagent and silyl enol ethers. In this reaction, zinc iodide, a by-product of the Simmons–Smith reaction, operates as a Friedel–Crafts-type catalyst to activate acid halides.

Synthesis of dibenzo[b,f]cycloprop[d]azepine derivatives. I. Introduction of a cyclopropane ring by the use of Simmons-Smith reagent.

The Simmons-Smith reaction of 5H-dibenz [b, f] azepine (4) and 5-methyl-5H-dibenz-[b, f] azepine (5) yielded 1, 1a, 6, 10b-tetrahydro-6-methyldibenzo [b, f] cycloprop [d] azepine (6), which represents synthesis of a novel condensed ring system. 6 was demethylated via the formamide derivative 7 to give 1, 1a, 6, 10b-tetrahydrodibenzo [b, f] cycloprop [d]-azepine (8), which was converted into pharmacologically active 6-dialkylaminoalkyl (9) and 6-carbamoyl (17) derivatives. Cyclopropanation of 5-(3-halopropyl)-5H-dibenz [b, f] azepines (11) with the Simmons-Smith reagent, however, led to additional reactions in the side chain to yield 12, 13, 14, and 15.

ChemInform Abstract: SOME CARBENE REACTIONS ON MYRCENE

AbstractIn alkalischem Medium und in Gegenwart von Triäthylbenzylammoniumchlorid entsteht durch Addition des Dichlorcarbens aus Myrcen (II) das Diaddukt (I).

The cyclopropanation of silyl enol ethers. A powerful synthetic tool

Abstract

Unusual Simmons-Smith reaction affording noncyclopropyl compounds. New route to 2-methylenecycloalkanols from silyl alkenyl ethers

Bei der Reaktion der Cycloalkenyltrimethylsilylather (I) mit Methylenjodid (II) nach Simmons-Smith erhalt man in Gegenwart von Zn-Cu die Cyclopropane (III), die mit Wasser zu den Carbinolen (IV) verseift werden.

Reaction of trimethysilyl enol ethers with Simmons-Smith reagent. Facile synthesis of trimethylsilyl cyclopropyl ethers and cyclopropanols

Reaction of trimethysilyl enol ethers with Simmons-Smith reagent. Facile synthesis of trimethylsilyl cyclopropyl ethers and cyclopropanols

Fatty acids, part 40 the synthesis and chromatographic and spectroscopic properties of the disubstituted cyclopropanes derived from all the methyl trans-octadecenoates

All the methyl trans-methyleneoctadecanoates (cyclopropane compounds) have been prepared from the corresponding trans-octadecenoates by the Simmons-Smith reaction. Their GLC behaviour on DEGS and ApL columns and their NMR spectra are reported.

On the Active Organozinc Species in the Reaction of Zinc-Methylene lodide Reagents with Benzaldehyde

Zinc-methylene iodide reagents were prepared in THF from the various amounts of methylene iodide and zinc, and the reactiqns with benzaldehyde were examined. The zinc-methylene iodide reagent(reagent A)prepared by the reaction with more than 2 molar amounts of zinc did not afford methyl iodide on the hydrolysis, but gave methylene iodide on treatment with iodine (No.1, No.2 in Table 1). This observation seems to indicate that reagent A contained no ICH2Zn-unit b.ut-ZnCH2Zn-unit. Reagent A reacted with benzaldehyde to give styrene, but the Simmons-Smith reaction did not occur with the reagent.After the preparation of feagent A, the residual zinc was removed by ltration and an additional amount of methylene iodide was added to the reaction mixture. The mixture gave ethyl iodide on the hydrolysis, and norcarane in the reaction with cyclohexene(No.7), The reagent(reagent B)prepared from less than 1molar amount of zinc also gave norcarane with cyclohexene in poor yields, but styrene was not formed with benzaldehyde(No.3, No.4).These facts suggest that the active organozinc species which converts benzaldehyde into styrene may be represented as CH2(Znl)2. The presence of the following reversible reaction between the Simmons-Smith reagent ICH Znl, and theCH2(Znl)2is also suggested.

Cyclopropylcarbinyl-oxo-carbonium Ions. Part VI. Synthesis and Chemistry of an Epimeric Pair of Homoallyl Iodides (3-Iodomethyl Glycals)

The homoallyl iodide 4,6-O-benzylidene-1,2,3-trideoxy-D-ribo-hex-1-enopyranose, 4, is the second major product from Simmons–Smith reaction of methyl 4,6-O-benzylidene-2,3-dideoxy-α-D-erythro-hex-2-enopy-ranoside, 6α. The major product is the cyclopropyl glycoside 7α, which when treated separately with the Simmons–Smith reagents furnishes an 85% yield of 4. The mechanism of this transformation is investigated. It is not simply a Lewis-catalyzed iodinolysis since zinc iodide in a variety of solvents does not convert 7α to 4. Methylene iodide is essential, as is the organo-zincate complex, operative in Simmons–Smith reactions.The 3-epimer of the homoallyl iodide 4, i.e. 4,6-O-benzylidene-1,2,3-trideoxy-D-arbino-hex-1-enopyranose, 5, is produced in only 0.9% yield in the methylenation of the anomeric olefinic glycoside, 6β. The low yield is attributable to the extensive anomerization experienced by 6β itself, and by the primary reaction products. This leads to a plethora of compounds including both epimeric homoallyl iodides 4 and 5.In order to get it all together, the homoallyl iodide 4 is transformed into its epimer 5 by an unambiguous synthetic sequence. Some of the intermediates in this sequence are polyfunctional molecules of considerable synthetic potential.The possibility of an alternative route to compound 4 directly from the olefinic glycoside 6α is discussed. Coordination of the methoxyl oxygen of 6α to the organo-zincate complex could achieve an ideal SNi transition state in which [Formula: see text] is delivered at C-3 with synchronous departure of the methoxyl group. This mechanism, called the "reverse" allylic rearrangement for reasons outlined in the text, is discussed.

Conformational aspects of the directive effect of the homoallylic hydroxyl group in the Simmons-Smith reaction

Conformational aspects of the directive effect of the homoallylic hydroxyl group in the Simmons-Smith reaction

Reactivity of co-ordinated ligands. Part VII. Electrophilic substitution and addition reactions of co-ordinated cycloheptatriene

Under Friedel–Crafts conditions, with acetyl chloride and aluminium trichloride, tricarbonyl(cycloheptatriene)iron undergoes both electrophilic addition and substitution to give tricarbonyl(2–6-η-1-acetylcycloheptadienium)iron, isolated as the hexafluorophosphate salt, and tricarbonyl(1-acetylcyclohepta-1,3,5-triene)iron. Reaction of tricarbonyl(cycloheptatriene)iron with acyl tetrafluoroborates (RCO)BF4(R = Me or Ph) yields only addition salts of the tricarbonyl(2–6-η-1-acetylcycloheptadienium)iron type. These salts react with methoxide ion to give the ethers, tricarbonyl(1-acyl-6-methoxycyclohepta-2,4-diene)iron, which readily undergo 1,2-elimination of methanol on silica gel to yield substitution products. Formylation of tricarbonyl(cycloheptatriene)iron produces tricarbonyl(formylcycloheptatriene)iron. This aldehyde is readily reduced to the corresponding primary alcohol. This alcohol on treatment with hexafluorophosphoric acid gives tricarbonyl(2–6-η-1-methylenecycloheptadienium)iron hexafluorophosphate which contains an exocyclic double bond. The acetyl and formyl derivatives undergo protonation in acid media yielding ring and oxygen protonated species respectively. Reaction of tricarbonyl(cycloheptatriene)iron with the Simmons–Smith reagent produces hexacarbonyl[bi(cyclohepta-2,4,6-trienyl)]di-iron by hydrogen abstraction. The stereochemistry of the electrophilic addition to tricarbonyl(cycloheptatriene)iron is discussed.

The Effect of Some 3-Oxygen Functions on the Simmons–Smith Methylenation of 5,6-Unsaturated Steroids

The effect of 3α- and 3β-hydroxy, 3α- and 3β-acetoxy, 3-ethylene acetal, and 3α-methoxy derivatives of 5-cholestene on the addition of the Simmons–Smith reagent to the steroidal 5,6-double bond has been investigated. Reaction occurred only with epi-cholesterol to yield chiefly 3α-hydroxy-5,6α-cyclopropano-5α-cholestane. The 3α-ethyl ether, 3α-acetate, and a dialkoxymethane have been identified as byproducts. The p.m.r. and mass spectral data are given.

Replacement of the carbonyl oxygen of hydroxy ketones by methylene and 1,1-ethano groups by reaction with the Simmons-Smith reagent

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReplacement of the carbonyl oxygen of hydroxy ketones by methylene and 1,1-ethano groups by reaction with the Simmons-Smith reagentI. T. Harrison, R. J. Rawson, P. Turnbull, and J. H. FriedCite this: J. Org. Chem. 1971, 36, 23, 3515–3517Publication Date (Print):November 1, 1971Publication History Published online1 May 2002Published inissue 1 November 1971https://doi.org/10.1021/jo00822a010RIGHTS & PERMISSIONSArticle Views181Altmetric-Citations21LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (409 KB) Get e-Alerts Get e-Alerts

Methylene-insertion reactions with unsaturated sugars. Synthesis of 4- C-cyclopropyl- d- ribo-tetrofuranose derivatives

3- O-Benzyl-5,6-dideoxy-1,2- O-isopropylidene-α- d- xylo-hex-5-enofuranose ( 1) was converted by the Simmons-Smith reaction into the cyclopropyl derivative 2, which was debenzylated to the known 2 4- C-cyclopropyl-1,2- O-isopropylidene-α- d- xylo-tetrofuranose ( 3). Oxidation of 3 with ruthenium tetraoxide gave the corresponding 3-ketone 4, which underwent stereospecific reduction by borohydride to give 4- C-cyclopropyl-1,2- O-isopropylidene-α- d- ribo-tetrofuranose ( 6). In an alternative route to 6, 3- O-benzyl-1,2- O-isopropylidene-α- d-allofuranose ( 10) was prepared by a high-yielding procedure and converted into 3- O-benzyl-5,6-dideoxy-1,2- O-isopropylidene-α- d- ribo-hex-5-enofuranose ( 12), either by way of an orthoformate ( 11) or thionocarbonate ( 14) intermediate; the alkene 12 was then converted into the cyclopropyl derivative 15, and 15 was subsequently debenzylated to give 6. 1,2- O-Isopropylidene-α- d-allofuranose ( 7) was converted, either by way of the 5,6-thiono-carbonate 8 or an orthoformic ester, into 5,6-dideoxy-1,2- O-isopropylidene-α- d- ribo-hex-5-enofuranose ( 9). High yields were achieved in all steps, and n.m.r. spectral data are given for the products. Mass-spectral data are given for the ketone 4, the cyclopropyl derivative 6, the thionocarbonate 8, and the alkenes 9 and 12; o.r.d. and c.d. data are also given for the thionocarbonates 8 and 14.