Stereospecific synthesis and absolute configuration of optically active diaryl(acyloxy)(alkoxy)spiro-λ4-sulfanes

✍ Scribed by Dénes Szabó; Szilárd Szendeffy; István Kapovits; Árpád Kucsman; Mátyás Czugler; Alajos Kálmán; Péter Nagy

• Book ID: 104361261
• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Weight: 601 KB
• Volume: 8
• Category: Article
• ISSN: 0957-4166
• DOI: 10.1016/s0957-4166(97)00245-0

✦ Synopsis

Optically active (R)-(+)-l,l '-spirobi[3H-2,1-benzoxathiol]-3-one (R)-(+)-5, the (R)-(+) and (S)-(-) enantiomers of spiro [3H-2,1-benzoxathiol-l,l'-naphtho[1,8-d,e]-3H-2,1-oxathiin-3-one] (R)-(+)-8 and (S)-(-)-8, and (S)-(+)-spiro [3H-2,l-benzoxathiol-3-one-l,l'-naphtho[1,8-d,e]-3H-2,1-oxathiine] (S)-(+)-10 all belonging to the class of diaryl(acyloxy)-(alkoxy)spiro-~4-sulfanes (spirosulfuranes) were prepared by dehydration of the optically active diaryl sulfoxides (R)-(+)-4, (R)-(-)-7, (S)-(+)-7, and (S)-(+)-9, respectively, all of them carrying reactive CH2OH and COOH substituents. (R)-(+)-5H,7Hdibenzo[c,f]-l,5-oxathiocin-5-one 12-oxide (R)-(+)-6, a sulfoxide-lactone isomer of spiro-~k4-sulfane (R)-(+)-5 was also obtained from (R)-(+)-4 by dehydration. The molecular structures including the absolute configurations were determined for (R)-(+)-5, (R)-(+)-6 and (R)-(+)-8 by X-ray diffraction method. Relevant bond length and angle data are listed. Sulfur configurations, solid-state conformations and a stereospecific pathway for the dehydration of sulfoxides are discussed in detail.