Departament of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneve 4, Switzerland, Department of Organic Chemistry, Stockholm University, Arrhenius Laboratoriet, 106 91 Stockholm, Sweden, Organic Chemistry II, Dormund University of Technology, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany, and Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, C/ Marcel · li Domingo s/n, 43007 Tarragona, Spain

Enantioselective Copper-Catalyzed Conjugate Addition and Allylic Substitution Reactions

Progress in the synthesis and transformations of alkylidenecyclopropanes and alkylidenecyclobutanes.

An efficient kinetic resolution of sulfoximines with enals was realized using chiral N-heterocyclic carbene (NHC) catalysts. The stereoselective amidation proceeds without additional acyl transfer agent. Both enantiomers of the sulfoximines can be obtained with excellent ee values (up to 99% ee and −97% ee, respectively). Performing the catalysis on a gram scale allowed using the recovered sulfoximine (+)-1j in an asymmetric synthesis of FXa inhibitor F.

Organocatalytic Kinetic Resolution of Sulfoximines

Sulfoximine-substituted bis(allyl)titanium complexes, which are configurationally labile at the Cα-atoms, have emerged as valuable reagents in asymmetric synthesis. Their highly selective reactions with aldehydes and N-sulfonyl imino esters allow the attainment of enantio- and diastereomerically pure sulfoximine-substituted homoallylic alcohols and homoallylic amines, respectively, which are valuable starting materials for the asymmetric synthesis of homopropargylic alcohols, 2,3-dihydrofurans, medium-sized carbocycles and lactones, unsaturated mono- and bicyclic prolines, β-amino acids, and vinyl oxiranes, respectively. The high synthetic versatility of the sulfoximine group stems from its ability to function as a chiral carbanion-stabilizing nucleofuge. © 2007 Wiley Periodicals, Inc. 18:472–481, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20331

Development of new methods for asymmetric synthesis based on sulfoximines

Regioselectivity of the Reactions of Heteroatom-Stabilized Allyl Anions with Electrophiles.

Regio- and Enantioselective Substitution of Primary Endocyclic Allylic Sulfoximines with Organocopper and Organocuprate Reagents. The Importance of Iodide for the Allylic Substitution with Organocopper Compounds

Enantiomerically pure N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(phenyl)cinnamylsulfoximines as well as the corresponding crotylsulfoximines have been prepared from N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(lithiomethyl)sulfoximines and carbonyl compounds by an addition-elimination-isomerization reaction sequence. Under basic conditions, complete isomerization of the vinylic sulfoximines, obtained as intermediates, to the corresponding allylic sulfoximines takes place. Chromatographically separable mixtures of (E) and (Z) allylic sulfoximines were isolated in the case of beta,gamma-disubstituted allylic sulfoximines. The (E/Z) ratio depends on the nature of the substituents in the beta- and gamma-positions, and the equilibrium amount of the (Z) isomer varies from 68% to nil. The allylic N-methylsulfoximines do not racemize thermally, and their rearrangement to the corresponding allylic sulfinamides is negligible. Upon prolonged treatment with boron trifluoride at low temperatures allylic N-methylsulfoximines are recovered unchanged. The crystal structure of S-(3,4-dihydronaphthalen-2-ylmethyl)-N-methyl-S-phenylsulfoximine was determined. Reaction of the allylic sulfoximines with butylcopper in the presence of lithium iodide and boron trifluoride leads with very high gamma-selectivities and moderate to high enantioselectivities to the corresponding chiral alkenes. Their configuration was determined by chemical correlation through ozonolysis to the corresponding carbonyl compounds. The asymmetric induction exerted by the chiral N-methyl-S-phenylsulfoximine group strongly depends on the double bond configuration and the substituents in the beta- and gamma-positions. The (E) allylic sulfoximines are substituted with low to moderate enantioselectivities (2-66%), whereas the (Z) allylic sulfoximines react with much higher enantioselectivities (69-92%). Interestingly, substitution of the beta-methyl-gamma-phenyl-substituted (Z) allylic sulfoximine and its beta-phenyl-gamma-methyl isomer proceeded with almost the same degree of asymmetric induction but with the opposite sense. Replacement of the N-methyl group by a benzyl or a methoxyethyl group has no significant influence on the regio- and enantioselectivity of the substitution.

Regio- and Enantioselective Substitution of Acyclic Allylic Sulfoximines with Butylcopper in the Presence of Lithium Iodide and Boron Trifluoride.

Rearrangement of allylic sulfoximines to allylic sulfinamides

Thermolysis of the enantiomerically pure allylic sulfoximines 3a,b leads to their partial rearrangement to the isomeric allylic sulfinamides 5a,b and 6a,b, respectively, with complete retention of configuration at the S-atom. Racemization of the allylic sulfoximines 3a,b at the S-atom does not occur.

Rearrangement of Allylic Sulfoximines to Allylic Sulfinamides.

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Regio- and Enantioselective Substitution of Primary Endocyclic Allylic Sulfoximines with Organocopper and Organocuprate Reagents. The Importance of Iodide for the Allylic Substitution with Organocopper Compounds

Regio- and Enantioselective Substitution of Acyclic Allylic Sulfoximines with Butylcopper in the Presence of Lithium Iodide and Boron Trifluoride.

Rearrangement of allylic sulfoximines to allylic sulfinamides

Regio- and Enantioselective Substitution of Acyclic Allylic Sulfoximines with Butylcopper in the Presence of Lithium Iodide and Boron Trifluoride.

Rearrangement of Allylic Sulfoximines to Allylic Sulfinamides.