Simmons-Smith Research Articles

ChemInform Abstract: Diastereo-Differentiating Simmons-Smith Reaction Using a New Chiral Auxiliary.

Abstract Diastereo-differentiating Simmons-Smith reactions of enol ethers of various ketones were carried out by using (3 S ,5 S )-2,6-dimethyl-3,5-heptanediol as a new chiral auxiliary. The diastereomer excess of these reactions reached to be >99%.

ChemInform Abstract: Polarized Ketene S,S‐Acetals. Part 81. Attempted Simmons‐Smith Reaction on α‐Oxo Ketene Dithioacetals: A New General Route to 3,4‐Substituted and Anellated Thiophenes.

ChemInformVolume 21, Issue 5 Heterocyclic Compounds ChemInform Abstract: Polarized Ketene S,S-Acetals. Part 81. Attempted Simmons-Smith Reaction on α-Oxo Ketene Dithioacetals: A New General Route to 3,4-Substituted and Anellated Thiophenes. A. THOMAS, A. THOMAS North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorG. SINGH, G. SINGH North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorH. ILA, H. ILA North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorH. JUNJAPPA, H. JUNJAPPA North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this author A. THOMAS, A. THOMAS North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorG. SINGH, G. SINGH North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorH. ILA, H. ILA North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this authorH. JUNJAPPA, H. JUNJAPPA North-Eastern Hill Univ., Shillong-793003, Meghalaya, IndiaSearch for more papers by this author First published: January 30, 1990 https://doi.org/10.1002/chin.199005166Read 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. Volume21, Issue5January 30, 1990 RelatedInformation

Tritiated methylene diiodide: a new synthetic labelling reagent

A simple synthesis of tritiated or deuteriated methylene diiodide is reported, providing a useful reagent for the incorporation of tritium or deuterium into a cyclopropyl ring through the Simmons–Smith reaction, as illustrated by regiospecific addition to perillyl alcohol.

A total synthesis of(+)-hirsutic acid.

The first asymmetric total synthesis of (+)-hirsutic acid has been accomplished in a highly stereocontrolled manner, including a novel method for the preparation of (1S, 5R, 6S)-6-hydroxy-cis-bicyclo[3.3.0]octan-3-one and a stereospecific Simmons-Smith reaction controlled by the participation of a relatively remote hydroxyl group.

ChemInform Abstract: Diastereo‐Differentiating Simmons‐Smith Reaction Using 2,4‐Pentanediol as a Chiral Auxiliary.

Abstract Diastereo-differentiating Simmons-Smith reaction to (1′ R , 3′ R ,)-1- (3′-hydroxy-1′-methylbutyloxy) cyclohexene has been performed to give (1′ R , 3′ R , 1 S , 6 S )-1-(3′-hydroxy-1′-methylbutyloxy) bicyclo [4.1.0] heptane in 95.2% d.e.

Diastereo-differentiating Simmons-Smith reaction using a new chiral auxiliary

Simmons-Smith reaction using a new chiral auxiliary shown in Scheme has been performed in over 99% d.e..

Attempted Simmons-Smith reaction on α-oxoketene dithioacetals: A new general route to 3,4-substituted and annelated thiophenes

A new general method for 3,4-substituted and annelated thiophenes through intramolecular cyclocondensation of a sulphonium ylid intermediate under Simmons-Smith reaction conditions on α-oxoketene dithioacetals has been reported.

Generation of spirocyclic quaternary centres via a tandem free radical cyclopropylcarbinyl rearrangement–cyclisation strategy

Regio- and stereo-specific construction of spirocyclic quaternary centres may be achieved by hydroxy-directed Simmons–Smith cyclopropanation of an allylic alcohol followed by a tandem free radical cyclopropylcarbinyl rearrangement–cyclisation reaction; generation of the spiro-fused systems is subject to stereoelectronic and kinetic control.

The Cyclopropane-Mediated Ring-Expansion of [4.3.1]Propellenes. A New Route to [5.3.1]Propelladienes

The [5.3.1] propelladiene (1) has been synthesized in six steps from the readily available [4.3.1] propellene (10a). Epoxidation of (10a) gives oxide (11a) which undergoes base-promoted rearrangement to allylic alcohol (12a). Simmons-Smith cyclopropanation of (12a) then gives the tetracyclic alcohol (13a). Mild thermolysis of the derived mesylate (14a) affords the ring-expanded isomer (20) which reacts with 1,8-diazabicyclo [5.4.0]undec-7-ene to give diene (1). A similar sequence of reactions has been used in the preparation of dienol (2) from acetal (10b). Compounds (1) and (2) react with 4-phenyl-4H-1,2,4-triazoline- 3,5-dione to give the Diels-Alder adducts (29a) and (29b) respectively.

Diastereo-differentiating simmons-smith reaction using 2,4-pentanediol as a chiral auxiliary

Diastereo-differentiating Simmons-Smith reaction to (1′ R , 3′ R ,)-1- (3′-hydroxy-1′-methylbutyloxy) cyclohexene has been performed to give (1′ R , 3′ R , 1 S , 6 S )-1-(3′-hydroxy-1′-methylbutyloxy) bicyclo [4.1.0] heptane in 95.2% d.e.

ChemInform Abstract: Reaction of Vinylidenecyclopropane with Simmons‐Smith Reagent Activated by Ultrasound.

AbstractUnder ultrasound the reaction between vinylidenecyclopropane (I) and Simmons‐Smith reagent (II) affords the expected products (III) and (IV) along with the cyclobutene (V).

ChemInform Abstract: 2‐Methyl‐5,6‐dihydro‐2H‐pyran in the Simmons‐Smith Reaction.

ChemInformVolume 18, Issue 46 Heterocyclic Compounds ChemInform Abstract: 2-Methyl-5,6-dihydro-2H-pyran in the Simmons-Smith Reaction. U. G. IBATULLIN, U. G. IBATULLIN Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorT. F. PETRUSHINA, T. F. PETRUSHINA Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorYU. N. POPOV, YU. N. POPOV Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorR. R. GATAULLIN, R. R. GATAULLIN Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorM. G. SAFAROV, M. G. SAFAROV Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this author U. G. IBATULLIN, U. G. IBATULLIN Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorT. F. PETRUSHINA, T. F. PETRUSHINA Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorYU. N. POPOV, YU. N. POPOV Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorR. R. GATAULLIN, R. R. GATAULLIN Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this authorM. G. SAFAROV, M. G. SAFAROV Bashkirskii gos. univ. im. 40-letiya Oktyabrya, Ufa 450074Search for more papers by this author First published: November 17, 1987 https://doi.org/10.1002/chin.198746261Read 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume18, Issue46November 17, 1987 RelatedInformation

ChemInform Abstract: Diastereoselective Cyclopropanation via Homochiral Ketals. Dioxolane Structural Effects.

Abstract A series of 2-cyclohexen-1-one ketals related to 2-cyclohexen-1-one 1,4-di- O -benzyl-L-threitol ketal but possesing different dioxolane appendages was prepared and subjected to Simmons-Smith cycloproponation. The observed diastereoselectivity decreased when oxygen was present in the appendages. In the absence of appendage oxygen, the sense of the observed diastereoselectivity was found to depend upon dioxolane chirality. The amount of diastereoselectivity observed was remarkably independent of the nature of the appendages.

2-Methyl-5,6-dihydro-2H-pyran in the simmons-smith reaction

2-Methyl-5,6-dihydro-2H-pyran reacts with the Simmons-Smith reagent to give a mixture of 2-ethyl-5,6-dihydro-2H-pyran, cis- and trans-2-methyl-3-oxabicyclo-[4.1.0]heptanes, and 2-methyl-2,5,6,7- or 3-methyl-2,3,6,7-tetrahydrooxepine in a ratio of 2∶2∶5∶1.

Ultrasound in lipids. Furan formation under ultrasonic assisted Simmons–Smith reaction and the effect of cadmium and copper as zinc replacers

Methyl 12-oxo-octadec-9-cis-enoate gave methyl 9,12-epoxyoctadeca-9,11-dienoate when treated with zinc or cadmium in the presence of di-iodomethane and 1,2-dimethoxyethane under concomitant ultrasonic irradiation, while under similar conditions copper caused cyclopropanation across the ethylenic bond in methyl oleate and ricinoleate.

Diastereoselective cyclopropanation via homochiral ketals. Dioxolane structural effects

A series of 2-cyclohexen-1-one ketals related to 2-cyclohexen-1-one 1,4-di- O-benzyl-L-threitol ketal but possesing different dioxolane appendages was prepared and subjected to Simmons-Smith cycloproponation. The observed diastereoselectivity decreased when oxygen was present in the appendages. In the absence of appendage oxygen, the sense of the observed diastereoselectivity was found to depend upon dioxolane chirality. The amount of diastereoselectivity observed was remarkably independent of the nature of the appendages.

Homochiral ketals in organic synthesis. Diastereoselective cyclopropanation of α,β-unsaturated ketals derived from 1,4-D1- [formula omitted]-benzyl-l-threitol

2-Cycloalken-1-one 1,4-di - O -benzyl -L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. For example, 2-cyclohexen-1-one 1,4-di - O -benzyl -L-threitol ketal gave in 90-98% yield a 9:1 mixture of diastereomeric cyclopropanes as established by 62.9 MHz 13C NMR spectroscopy and by hydrolysis of the mixture to (1 R ,6 S )-bicyclo[4.1.0] heptan-2-one. Sixteen other examples are presented which demonstrate the generality and predictability of the process for 2-cycloalken-1-one ketals, as wall as an unfortunate lack of diastereoselectivity for α,β-unsaturated 1,4-di- O -benzyl-L-threitol acetals.

Asymmetric simmons-smith reactions using homochiral protecting groups

Asymmetric Simmons-Smith reactions of α,β-unsaturated acetals derived from chiral dialkyl tartrate or (2 R ,4 R )-2,4-pentanediol are described. Treatment of the acetal with diethylzinc and methylene iodide gives a cyclopropane with high diastereoselectivity. The acetal group is readily transformed to the aldehyde or the ester group. In addition, the method is successfully applied to the enantioselective synthesis of 5,6-methanoleukotriene A 4, a stable and selective inhibitor of leukotriene biosynthesis.

An asymmetric Simmons-Smith reaction

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAn asymmetric Simmons-Smith reactionIsao Arai, Atsunori Mori, and Hisashi YamamotoCite this: J. Am. Chem. Soc. 1985, 107, 26, 8254–8256Publication Date (Print):December 1, 1985Publication History Published online1 May 2002Published inissue 1 December 1985https://doi.org/10.1021/ja00312a072RIGHTS & PERMISSIONSArticle Views1245Altmetric-Citations102LEARN 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 (395 KB) Get e-Alerts Get e-Alerts

13C magnetic resonance studies. 120. The Simmons–Smith reaction with some silyl enol ethers. Unusual ring expansions of some norcamphorsti

Unexpected difficulties with Simmons–Smith cyclopropanation of the trimethylsilyl enol ether of exo-tricyclo[3.2.1.02,4]-octan-6-one led to a reexamination of this reaction with the parent norcamphor derivative which under "concentrated" conditions gave ring-expanded allylic ethers in low yield. With the tert-butyldimethylsilyl ethers, however, the allylic product is formed in high yield in the norcamphor and exo-trimethylenenorcamphor (tricyclo[5.2.1.02,6]decan-8-one) systems. The tert-butyldimethylsilyl enol ethers of bicyclo[3.2.1]octan-6-one and nopinone do not undergo ring expansion under similar conditions but the silyl ether of 3-methylenenopinol is a major product in the latter case.