| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1345180 | Tetrahedron: Asymmetry | 2007 | 8 Pages |
The antipodes of 1-aryl-, 1-alkyl- and 1-alkoxy-3-methyl-3-phospholene 1-oxides 1a–h and 1-phenyl-3-methyl-3-phospholene 1-sulfide 1i were separated in good yields and high enantiomeric excesses (up to >99% ee) by resolution via formation of diastereomeric complexes with either (−)-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane 2 (TADDOL) or (−)-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol 3. The stereostructure of the supramolecular formations and the absolute configurations of the 3-phospholene oxides 1a, 1e and 1f were elucidated by single crystal X-ray crystallography. CD spectroscopy was also useful in determining the absolute configurations of some phospholene oxides 1b, 1c, 1g and 1h.
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(−)-[(S)-1-Phenyl-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC45H47O5PEe = 99%[α]D20=-56.0 (c 1, CHCl3)Absolute configuration: (S,2R,3R)
(−)-[(S)-1-(2-Methylphenyl)-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC46H49O5PEe >99%[α]D20=-57.7 (c 1, CHCl3)Absolute configuration: (S,2R,3R)
(−)-[(S)-1-(4-Methylphenyl)-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC46H49O5PEe >99%[α]D20=-59.7 (c 1, CHCl3)Absolute configuration: (S,2R,3R)
(−)-[1-Naphthyl-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC49H49O5PEe >99%[α]D20=-59.5 (c 1, CHCl3)Absolute configuration: (2R,3R)
(−)-[(R)-1-Ethyl-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC41H47O5PEe = 58%[α]D20=-55.5 (c 1, CHCl3)Absolute configuration: (R,2R,3R)
(−)-[(R)-1-Propyl-3-methyl-3-phospholene 1-oxide-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane] complexC41H45O5PEe = 95%[α]D20=-48.0 (c 1, CHCl3)Absolute configuration: (R,4R,4R)
(−)-[(R)-1-Ethoxy-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC41H47O6PEe = 95%[α]D20=-54.4 (c 1, CHCl3)Absolute configuration: (R,2R,3R)
(−)-[(R)-1-(Isopropoxy)-3-methyl-3-phospholene 1-oxide-(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC42H49O6PEe >99%[α]D20=-65.5 (c 1, CHCl3)Absolute configuration: (R,2R,3R)
(−)-[1-Phenyl-3-methyl-3-phospholene 1-sulfide-2∗(2R,3R)-α,α,α′,α′-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol] complexC79H81O8SPEe >99%[α]D20=-65.2 (c 1, CHCl3)Absolute configuration: (2R,3R)
(−)-(S)-1-Phenyl-3-methyl-3-phospholene 1-oxideC11H13OPEe = 99%[α]D20=-37 (c 1, CHCl3)Absolute configuration was determined by X-ray analysisAbsolute configuration: (S)
(−)-(S)-1-(2-Methylphenyl)-3-methyl-3-phospholene 1-oxideC12H15OPEe >99%[α]D20=-28.6 (c 1, CHCl3)Absolute configuration was determined by CD spectroscopyAbsolute configuration: (S)
(−)-(S)-1-(4-Methylphenyl)-3-methyl-3-phospholene 1-oxideC12H15OPEe >99%[α]D20=-39.1 (c 1, CHCl3)Absolute configuration was determined by CD spectroscopyAbsolute configuration: (S)
(−)-1-Naphthyl-3-methyl-3-phospholene 1-oxideC15H15OPEe >99%[α]D20=-40.9 (c 1, CHCl3)Absolute configuration was not determined
(+)-(R)-1-Ethyl-3-methyl-3-phospholene 1-oxideC7H13OPEe = 58%[α]D20=+8.7 (c 1, CHCl3)Absolute configuration was determined by X-ray analysisAbsolute configuration: (R)
(+)-(R)-1-Propyl-3-methyl-3-phospholene 1-oxideC8H15OPEe = 95%[α]D20=+13.4 (c 1, CHCl3)Absolute configuration was determined by X-ray analysisAbsolute configuration: (R)
(−)-(R)-1-Ethoxy-3-methyl-3-phospholene 1-oxideC7H13O2PEe = 95%[α]D20=-10.6 (c 1, CHCl3)Absolute configuration was determined by CD spectroscopyAbsolute configuration: (R)
(−)-(R)-1-(Isopropoxy)-3-methyl-3-phospholene 1-oxideC8H15O2PEe >99%[α]D20=-15.6 (c 1, CHCl3)Absolute configuration was determined by CD spectroscopyAbsolute configuration: (R)
(+)-1-Phenyl-3-methyl-3-phospholene 1-sulfideC11H13SPEe >99%[α]D20=+7.8 (c 1, CHCl3)Absolute configuration was not determined
