Synthesis and reactions of the optically active selenols derived from monoterpenes

A convenient methodology for the synthesis of optically active selenols, derived from p-menthane, carane, and pinane, is described. The selenols were oxidized with air to give the optically active diselenides, and were also converted into the corresponding allylic selenides via reaction with Z- and E-cinnamyl, geranyl, and neryl chlorides. Oxidation of the allylic selenides with mCPBA gave the optically active alcohols via [2,3]-sigmatropic rearrangement of the in situ generated allylic selenoxides.

Figure optionsDownload as PowerPoint slide

(1S,2S,5R)-(+)-Neomenthyl selenolC10H20SeEe >99%[α]D20=+47.54 (c 1.61, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1S,2S,5R)

(1R,2S,5R)-(−)-Menthyl selenolC10H20SeEe >99%[α]D20=-50.8 (c 0.94, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1R,2S,5R)

(1S,3R,4S,6R)-(+)-Caranyl selenolC10H18SeEe >99%[α]D20=+6.6 (c 2.76, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4S,6R)

(1S,3R,4R,6R)-(−)-Isocaranyl selenolC10H18SeEe >99%[α]D20=-151.9 (c 1.07, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4R,6R)

(1S,2R,5S)-(−)-cis-Myrtanyl selenolC10H18SeEe >96%[α]D20=-46.9 (c 0.98, CHCl3)Source of chirality: (−)-β-PineneAbsolute configuration: (1S,2R,5S)

(1S,2S,3R,5R)-(−)-Pinocamphyl selenolC10H18SeEe >99%[α]D20=-28.2 (c 1.65, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3R,5R)

(1S,2S,3S,5R)-(+)-Isopinocamphyl selenolC10H18SeEe >99%[α]D20=+37.8 (c 0.93, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3S,5R)

(1S,2S,5R)-(+)-(E)-Cinnamyl neomenthyl selenideC19H28SeEe >99%[α]D20=+165.5 (c 1.41, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1S,2S,5R)

(1R,2S,5R)-(−)-(E)-Cinnamyl menthyl selenideC19H28SeEe >99%[α]D20=-123.2 (c 1.66, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1R,2S,5R)

(1S,3R,4S,6R)-(+)-(E)-Cinnamyl 4-caranyl selenideC19H26SeEe >99%[α]D20=+55.5 (c 1.74, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4S,6R)

(1S,3R,4R,6R)-(−)-(E)-Cinnamyl 4-isocaranyl selenideC19H26SeEe >99%[α]D20=-79.2 (c 1.71, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4R,6R)

(1S,2R,5S)-(−)-(E)-Cinnamyl cis-myrtanyl selenideC19H26SeEe >96%[α]D20=-35.7 (c 1.66, CHCl3)Source of chirality: (−)-β-PineneAbsolute configuration: (1S,2R,5S)

(1S,2S,3R,5R)-(+)-(E)-Cinnamyl pinocamphyl selenideC19H26SeEe >99%[α]D20=+52.0 (c 1.70, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3R,5R)

(1S,2S,3S,5R)-(−)-(E)-Cinamyl isopinocamphyl selenideC19H26SeEe >99%[α]D20=-116.3 (c 1.51, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3S,5R)

(1S,2S,5R)-(+)-(Z)-Cinnamyl neomenthyl selenideC19H28SeEe >99%[α]D20=+138.9 (c 1.42, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1S,2S,5R)

(1R,2S,5R)-(−)-(Z)-Cinnamyl menthyl selenideC19H28SeEe >99%[α]D20=-133.3 (c 1.57, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1R,2S,5R)

(1S,3R,4S,6R)-(+)-(Z)-Cinnamyl 4-caranyl selenideC19H26SeEe >99%[α]D20=+61.9 (c 0.91, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4S,6R)

(1S,3R,4R,6R)-(−)-(Z)-Cinnamyl 4-izocaranyl selenideC19H26SeEe >99%[α]D20=-100.55 (c 0.90, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4R,6R)

(1S,2R,5S)-(−)-(Z)-Cinnamyl cis-myrtanyl selenideC19H26SeEe >96%[α]D20=-33.0 (c 1.68, CHCl3)Source of chirality: (−)-β-PineneAbsolute configuration: (1S,2R,5S)

(1S,2S,3R,5R)-(+)-(Z)-Cinnamyl pinocamphyl selenideC19H26SeEe >99%[α]D20=+43.0 (c 1.53, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3R,5R)

(1S,2S,3S,5R)-(−)-(Z)-Cinnamyl izopinocamphyl selenideC19H26SeEe >99%[α]D20=-95.2 (c 1.70 CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3S,5R)

(1S,2S,5R)-(+)-Geranyl neomenthyl selenideC20H36SeEe >99%[α]D20=+81.3 (c 1.23, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1S,2S,5R)

(1R,2S,5R)-(−)-Geranyl menthyl selenideC20H36SeEe >99%[α]D20=-81.9 (c 1.83, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1R,2S,5R)

(1S,3R,4R,6R)-(−)-4-Isocaranyl geranyl selenideC20H34SeEe >99%[α]D20=-69.3 (c 1.88, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4R,6R)

(1S,2R,5S)-(−)-Geranyl cis-myrtanyl selenideC20H34SeEe >96%[α]D20=-114.05 (c 1.61, CHCl3)Source of chirality: (−)-β-PineneAbsolute configuration: (1S,2R,5S)

(1S,2S,3R,5R)-(−)-Geranyl pinocamphyl selenideC20H34SeEe >99%[α]D20=-23.0 (c 1.57, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3R,5R)

(1S,2S,5R)-(+)-Neomenthyl neryl selenideC20H36SeEe >99%[α]D20=+48.0 (c 1.88, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1S,2S,5R)

C20H36Se(1R,2S,5R)-(−)-Menthyl neryl selenideEe >99%[α]D20=-63.0 (c 1.95, CHCl3)Source of chirality: (−)-MentholAbsolute configuration: (1R,2S,5R)

(1S,3R,4R,6R)-(−)-4-Isocaranyl neryl selenideC20H34SeEe >99%[α]D20=-89.4 (c 0.94, CHCl3)Source of chirality: (+)-3-CareneAbsolute configuration: (1S,3R,4R,6R)

(1S,2R,5S)-(−)-cis-Myrtanyl neryl selenideC20H34SeEe >96%[α]D20=-30.3 (c 1.89, CHCl3)Source of chirality: (−)-β-PineneAbsolute configuration: (1S,2R,5S)

(1S,2S,3S,5R)-(+)-Isopinocamphyl neryl selenideC20H34SeEe >99%[α]D20=+41.4 (c 1.85, CHCl3)Source of chirality: (−)-α-PineneAbsolute configuration: (1S,2S,3S,5R)