The cleavage of a strained propellane by transition metal carbonyls

Gassman, Paul G.; Armour, Eugene A.

doi:10.1016/s0040-4039(01)96729-2

Cited by 15 publications

(2 citation statements)

References 6 publications

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“…3b: 95% yield, oil; R, 0.20 (CHC13); NMR (CDC13) 1.22 (s, 9 ), 1.50 (s, 3 ), 1.67 (s, 3 H), 4.54 (s, 1 H), 5.33 (d, 1 H, J = 4.0 Hz), 5.56 (d, 1 H, J = 4.0 Hz), 5.78 (d, 1 H, C-9 , AB system, J = 5.6 Hz), 5.85 (d, 1 H, C-9 , AB system, J = 5.6 Hz).…”

Section: Methodsmentioning

confidence: 99%

Nucleophilic SN2 displacements on (pivaloyloxy)methyl 6.alpha.-[(fluorosulfonyl)oxy]penicillanate

Setti¹,

Mascaretti²

1986

J. Org. Chem.

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SrCI4/CH2CI2 or CHClj RN3 + (CH3 )3SiX Ns VR1.R2.R3 * H 2-R|-CH3; Rg.Rs-H 3*R1.R2*CH3:R3*H 4*Ri,R2, R3 * CK3 6 7 ff Q"' 8solvent to provide the corresponding azides. However, the reaction does not proceed with unactivated alkyl halides. We have found now in our studies that polycyclic adamantyl,20 diamantyl related halides and cyclic cyclohexyl and cyclopentyl halides react with trimethylsilyl azides under stannic chloride catalysis to give the corresponding azides in moderate to excellent yields (Table I).The reaction works well with both tertiary bridgehead as well as with secondary halides. This is significant, since secondary hydroxy compounds do not give the secondary azides directly using the NaN3/H2S04 method.1 23 4The presently developed procedure to prepare polycyclic and cyclic azides using readily available trimethylsilyl azide is superior to other existing methods for its convenience, good yields, and general applicability to both secondary and tertiary systems. Experimental SectionTo a stirred solution of the polycyclic or cyclic halide and trimethylsilyl azide23® (relative ratios in Table I) in 50 mL of dry dichloromethane or chloroform under nitrogen at 0 °C is added stannic chloride233 catalyst (see table for the exact amount). After the addition, the mixture was brought to room temperature followed by prolonged stirring or reflux for the stipulated period of time (Table I). After the reaction was complete the mixture was quenched with ice-water (100 mL) followed by methylene chloride or chloroform extraction (2 X 100 mL). The organic layer was dried over anhydrous MgS04 and evaporated to obtain the crude azide. The crude azide was further purified, when necessary, on a silica gel column using hexane-dichloromethane eluent (20:1) or fractional distillation. The purity of the product azide was confirmed by 13C NMR (Table I), IR, and melting point measurement.Acknowledgment. Support of our work by the National Institutes of Health is gratefully acknowledged.

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Section: Methodsmentioning

confidence: 99%

Nucleophilic SN2 displacements on (pivaloyloxy)methyl 6.alpha.-[(fluorosulfonyl)oxy]penicillanate

Setti¹,

Mascaretti²

1986

J. Org. Chem.

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“…1983, 4, 488. (b) Unpublished calculations with T. Clark show the problems of trying to go to higher level ah initio calculations but agree fully with the conclusions of Chen and Fox at the MNDO level. (9) Schlatmann, J. L. M. A.; Korsloot, J. G.; Schut, J. Tetrahedron 1972, 26, 949.…”

Section: Methodsmentioning

confidence: 99%