2‐Cyclohexenone

Gannon, Walter F.; House, Herbert O.

doi:10.1002/0471264180.os040.05

Cited by 4 publications

(4 citation statements)

References 9 publications

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“…The cyclohexenone monomer 10 with neither epoxy nor hydroxy functionalities was prepared according to Scheme 5. 3-Ethoxy-2cyclohexene-1-one (15) 13 was treated with LiCH 2 SPh 14 to afford 3-(phenylthiomethyl)-2-cyclohexen-1-one (16), which was converted to 3-formyl-2-cyclohexen-1-one (18) via Pummerer rearrangement. 15 Reduction with CeCl 3 -NaBH 4 , 16 oxidation with MnO 2 17 gave 3-(tert-butyldimethylsiloxymethyl)-2-cyclohexen-1-one (21).…”

Section: Resultsmentioning

confidence: 99%

“…Supporting Information Available: Complete experimental procedures, full characterization, copies of 1 H and 13 C NMR and IR of all new compounds, and Cartesian coordinates for calculated transition states of 6π-electrocyclization and Diels-Alder reaction (PDF). This material is available free of charge via the Internet at http://pubs.acs.org.…”

Section: Jo0355303mentioning

confidence: 99%

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Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

et al. 2004

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An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization.

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Section: Resultsmentioning

confidence: 99%

Section: Jo0355303mentioning

confidence: 99%

Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

et al. 2004

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“…(5) Convenient Synthesis of Substituted Cyclohexenone Derivatives from Cyclohexane-1,3-diones. The transformation of cyclohexane-1,3-diones to 2-cyclohexen-1-ones is well-known . Thus, we selected several diones such as 13 , 17 − 19 , and 22 , which were converted to enol ethers in a usual way.…”

Section: Resultsmentioning

confidence: 99%

Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks: Hidden Aspect of Thermodynamically Controlled Enolates

et al. 2001

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We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].

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“…To establish an ee determination method that is applicable for these elimination products a protocol comprising a reduction/elimination and oxidation reaction was used. Part of this protocol was actually developed for the synthesis of 2-cyclohexenones . Applying this protocol to the elimination products resulted in the formation of 23 in all cases.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Enantioselective Synthesis of (−)-Prostaglandin E₁ Methyl Ester Based on a Tandem 1,4-Addition−Aldol Reaction

et al. 2002

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Catalytic enantioselective 1,4-additions and tandem 1,4-addition-aldol reactions of dialkylzinc reagents to cyclopentene-3,5-dione monoacetals in the presence of an in situ generated Cu(OTf)(2)/chiral phosphoramidite catalyst result in highly functionalized cyclopentane building blocks with ee's up to 97%. A new synthesis of cyclopentene-3,5-dione monoacetals is presented as well as its use in a tandem 1,4-addition-aldol protocol for the catalytic asymmetric total synthesis of (-)-PGE(1) methyl ester. This synthesis represents a new approach to this class of natural products. By using only 3 mol % of an enantiomerically pure catalyst in the key step, the absolute configurations at three stereocenters of the basic structure of the PGE(1) are established at once.

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2‐Cyclohexenone

Abstract: 2‐Cyclohexenone product: 2‐cyclohexenone

Cited by 4 publications

References 9 publications

Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks: Hidden Aspect of Thermodynamically Controlled Enolates

Catalytic Enantioselective Synthesis of (−)-Prostaglandin E₁ Methyl Ester Based on a Tandem 1,4-Addition−Aldol Reaction

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2‐Cyclohexenone

Abstract: 2‐Cyclohexenone product: 2‐cyclohexenone

Cited by 4 publications

References 9 publications

Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks: Hidden Aspect of Thermodynamically Controlled Enolates

Catalytic Enantioselective Synthesis of (−)-Prostaglandin E1 Methyl Ester Based on a Tandem 1,4-Addition−Aldol Reaction

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Catalytic Enantioselective Synthesis of (−)-Prostaglandin E₁ Methyl Ester Based on a Tandem 1,4-Addition−Aldol Reaction