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Volumn 62, Issue 18, 1997, Pages 6326-6343

Synthesis and diastereoselective complexation of enantiopure sulfinyl dienes: The preparation of sulfinyl iron(0) dienes

Author keywords

[No Author keywords available]

Indexed keywords

1 SULFINYL 1,3,8,10 TETRAENE; ALKADIENE; UNCLASSIFIED DRUG;

EID: 9844234809     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970693a     Document Type: Article
Times cited : (63)

References (88)
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    • 1H NMR; the vinylic proton coupling constant of 6.7 Hz was consistent with cis stereochemistry.
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    • The structure of 6a was verified by an NOE experiment: irradiation of the vinyl proton at 6.6 ppm resulted in a 2.0% enhancement for the allylic methylene at 2.6 ppm
    • The structure of 6a was verified by an NOE experiment: irradiation of the vinyl proton at 6.6 ppm resulted in a 2.0% enhancement for the allylic methylene at 2.6 ppm.
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    • note
    • Treatment of 4b with divinylcuprate (derived from commercially available vinylmagnesium bromide) afforded a 62:38 mixture of (1Z)- and (1E)-sulfinyl dienes (in a 1.6:1 ratio) and sulfinylethene. Treatment with the corresponding cyanocuprate afforded (Z)-2-cyano-1- sulfinylethene (25%) and unreacted 4b (65%).
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    • note
    • 3.
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    • See ref 57b for references which describe the synthesis of commercially unavailable vinyl stannanes. For the stannane used to prepare 10g, see: Hutzinger, M. W.; Oehlschlager, A. C. J. Org. Chem. 1995, 60, 4595-4601. For the stannane used to prepare 10h, 10i, and 10l, see: Barrett, A. G. M.; Barta, T. E.; Flygare, J. A. J. Org. Chem. 1989, 54, 4246-4249.
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    • See ref 57b for references which describe the synthesis of commercially unavailable vinyl stannanes. For the stannane used to prepare 10g, see: Hutzinger, M. W.; Oehlschlager, A. C. J. Org. Chem. 1995, 60, 4595-4601. For the stannane used to prepare 10h, 10i, and 10l, see: Barrett, A. G. M.; Barta, T. E.; Flygare, J. A. J. Org. Chem. 1989, 54, 4246-4249.
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    • note
    • D = +216.1, c 0.74, acetone]).
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    • (1Z)-1-Sulfinyl dienes 10g,h,i are obtained as 30-35:1 mixtures containing minor amounts of the (1E) isomers which can be readily removed by silica gel chromatography. The origin of this slight loss of stereoselectivity would appear to be in the Stille coupling process; however, the mechanism by which it occurs remains unclear.
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    • See ref 4e for an example of coupling involving an aryl iodide and stennylvinyl sulfoxide 1. We have only been able to effect a coupling between stannylvinyl sulfoxide 19 and p-nitrophenyl iodide to afford the corresponding 1-sulfinyl styrene derivative in a 39% yield.
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    • note
    • 4 (5 mol %) and CuI (30 mol %)] completely failed. While use of benzene as the solvent gave disappointing product yields of 20 to 30%, an improvement to 54% was realized using 4:1 benzene/ triethylamine as the solvent.
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    • H3-H4 was determined to be 11.0 Hz and 10.8 Hz for 16a and 16b, confirming the cis stereochemistry of the 3,4-double bond of each compound.
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    • The iodohydrin was obtained as a 6:1 mixture of diastereomers which were inseparable by column chromatography
    • The iodohydrin was obtained as a 6:1 mixture of diastereomers which were inseparable by column chromatography.
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