Remote regio- and stereocontrol by the sulfinyl group: Diels–Alder reaction of sulfinyl dienols and 8,8-dimethylnaphthalene-1,4,5(8H)-trione

Diels–Alder cycloaddition of 8,8-dimethylnaphthalene-1,4,5(8H)-trione with diastereomeric hydroxysulfinyldienes proceeded with high yields and good π-facial and regioselectivities. The hydroxysulfoxide moiety controls the regio- and stereoselectivities, through hydrogen bonds in the suggested transition state.

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(2R,SR)-1-(p-Tolylsulfinyl)-3,5-heptadien-2-olC14H18O2S[α]D20=+132 (c 1.8, acetone)Absolute configuration: (2R,SR)

(5R,8S)-9,10-Dihydroxy-8-{(1R)-1-hydroxy-2-[(4-methylphenyl)-(R)-sulfinyl]ethyl}-4,4,5-trimethyl-5,8-dihydro-1(4H)-anthracenoneC26H28O5S[α]D20=+84 (c 1.79, acetone)Absolute configuration: (1R,5R,8S,SR)