Our interest in the chemistry of the sulfone functional group has centered around its unique 'amphoteric' nature. The inductive and anion-stabilizing properties of the sulfone moiety enables reactions typical of many withdrawing groups in organic chemistry, including functionalization of the a,b, and g-carbons of the vinylsulfone via conjugate addition/alkylation or metalation/alkylation. However, it is the sulfone's additional ability to serve as a leaving group that places it in an almost unique position in the arsenal of the synthetic chemist.
Recent publications:
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Synthesis via Vinyl Sulfones 82 Synthesis of Enantiopure Termini-Differentiated Heptane Stereotriads. Jiang W.; Lantrip, D.A.; Fuchs, P.L. Organic Lett. 2000, 2, 2181-2184. Enantiopure epoxy cycloheptenyl sulfones syn-7b and anti-7b are prepared in five high-yielding and stereospecific operations from 1,3-cycloheptadiene. These substrates serve as effective precursors for cis- and trans-substituted tetrahydrofurans (12, 10) which are segments of the antineoplastic agent IKD-8344.
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Synthesis via Vinyl Sulfones 83 Synthesis and Oxidation Reactions of Cycloheptatrienyl Sulfones. Tong, Z.W.; Chen, Y.Z.; Hentemann, M.F. ; Fuchs, P.L. Tetrahedron Lett. 2000, 41, 7795-7799. Inexpensive cycloheptatriene is regiospecifically converted to all three phenylsulfonyl substituted cycloheptatrienes. Epoxidation of these materials with achiral reagents is shown to be relatively regiospecific. Reasonable levels of enantiomeric excess (similar to 63,78%) are achieved by Sharpless asymmetric dihydroxylation of a pair of 3-substituted trienes. Crystallization of these sulfones provides the diols in enantiomeric excesses greater than 90%.
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Synthesis via Vinyl Sulfones 84 An Efficient and Convenient Synthesis of Enantiopure 4-(t-butyldimethylsilyloxy)-cyclohex-2-en-1-one: a Formal Synthesis of (±)-Mesembranol. Evarts, J.B, Jr.; Fuchs, P.L. Tetrahedron Lett. 2001, 42, 3673-3675. Inexpensive enantiopure (+)-limonene oxide 1 is converted to 4-(R)-(t-butyldimethylsilyloxy)-cyclohex-2-ene-1-one 2a. All isolated intermediates can be distilled obviating the need for chromatography. With 2a,b in hand, a formal synthesis of (±)-mesembranol 17 using vinyl triflate methodology is high yielding.
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Synthesis via Vinyl Sulfones 85 Economical and Environmentally Friendly Syntheses of 2-(Phenylsulfonyl)-1,3-cyclohexadiene and 2-(Phenylsulfonyl)-1,3-cycloheptadiene. Meyers, David J.; Fuchs, P.L. J. Org. Chem. 2002, 67, 200-204. A large-scale and inexpensive synthesis of dienes 1 and 2 has been developed via a four-step procedure starting with benzenethiol and the corresponding cyclic ketone. No chromatography is required.
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| 215. | Synthesis via Vinyl Sulfones 86 Synthesis of Enantiopure Five-Carbon Stereodiads Applicable for the Preparation of the Mycolactones. Tong, Z.; Ma, S.; Fuchs, P.L. J.Sulfur Chemistry 2004, 1, 1-7.
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| 214. | Synthesis via Vinyl Sulfones 87 gamma-Allyl Phosphinoyl Phenyl Sulfone (GAPPS): A Conjunctive Reagent for the Synthesis of EE, EZ, and ET 1,3 -Dienes. Li, X.; Lantrip, D.; Fuchs, P.L. J.Am.Chem.Soc. 2003, 125, 14262-14263.
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| 210. | Synthesis via Vinyl Sulfones 88 Synthesis of Termini-Differentiated 6-Carbon Stereotetrads: An Alkylative Oxidation Strategy for Preparation of the C21-C26 Segment of Apoptolidin. Chen, Y.; Evarts, J.B., Jr.; Torres, E.; Fuchs, P.L., Organic Lett. 2002, 4, 3571-3574.
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