1985
DOI: 10.1002/hlca.19850680518
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Stereoselective Synthesis of Masked Amino‐polyols via Osmylation of 4,5‐Dihydro‐5‐vinylisoxazoles

Abstract: Variously substituted 4,5-dihydro-5-vinylisoxazoles, obtained by regio-and stereospecific cycloaddition of nitrile oxides to dienes, undergo smooth Os0,-catalyzed cis-hydroxylation to give amino-polyol precursors. The reaction is 'anti'-selective, the diastereoisomeric ratios ranging from 73 :27 up to 2 99 :l. Thus, the cycloaddition/ osmylation sequence allows the control of the relative configuration of up to four contiguous asymmetric centers.A sulfoxide-mediated approach to enantiomerically pure compounds … Show more

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Cited by 14 publications
(4 citation statements)
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“…2-(2-Hydroxycyclopentylidene)ethanenitrile (1d). The general procedure was employed with 4d (117.3 mg in 1 mL of THF) followed by radial chromatography (2:3 EtOAc:hexanes) to provide 70.7 mg (60%) of 1d as an oil: IR (film) 2253, 3383 cm -1 ; 1 H NMR (CS 2 ) δ 1.83−2.10 (m, 2H), 2.21−2.31 (m, 1H), 2.37−2.46 (m, 2H), 2.92−3.00 (m, 2H), 4.74−4.78 (m, 1H), 5.70 (q, J = 2 Hz, 1H); 13 C NMR (CS 2 ) δ 22.2, 31.4, 36.5, 76.3, 93.9, 117.1, 173.2; MS m / e 124 (M + H). A hexanes solution of butyllithium (1.1 equiv, 1.45 M in hexanes) was added to a cold (−78 °C), THF solution (2 mL) of 1d (80.7 mg), followed after 10 min., by neat p -nitrobenzoyl chloride (134 mg).…”
Section: Methodsmentioning
confidence: 99%
“…2-(2-Hydroxycyclopentylidene)ethanenitrile (1d). The general procedure was employed with 4d (117.3 mg in 1 mL of THF) followed by radial chromatography (2:3 EtOAc:hexanes) to provide 70.7 mg (60%) of 1d as an oil: IR (film) 2253, 3383 cm -1 ; 1 H NMR (CS 2 ) δ 1.83−2.10 (m, 2H), 2.21−2.31 (m, 1H), 2.37−2.46 (m, 2H), 2.92−3.00 (m, 2H), 4.74−4.78 (m, 1H), 5.70 (q, J = 2 Hz, 1H); 13 C NMR (CS 2 ) δ 22.2, 31.4, 36.5, 76.3, 93.9, 117.1, 173.2; MS m / e 124 (M + H). A hexanes solution of butyllithium (1.1 equiv, 1.45 M in hexanes) was added to a cold (−78 °C), THF solution (2 mL) of 1d (80.7 mg), followed after 10 min., by neat p -nitrobenzoyl chloride (134 mg).…”
Section: Methodsmentioning
confidence: 99%
“…In addition, an allylic oxygen substituent appears to retard the rate of asymmetric dihydroxylation. 95 Brimacombe examined the asymmetric dihydroxylation of the carbohydrate-derived a,/3-unsaturated esters (entries [30][31][32][33][34][35][36][37][38]. In matched examples (entries 31 and 34), the diastereoselectivity was enhanced.…”
Section: Double Stereodifferentiationmentioning
confidence: 99%
“…Recovered starting material If was obtained as an oil. The product 7 (R1 = Meg(Me2CHCMeg)SiO(CH2)g) was also obtained as an oil; Rf 0.6 (20% ethyl acetate in hexane); [opD -17°(c 0.90, CHClg); NMR 6.88 (dd, J = 15.8 and 5.42 Hz, 1H), 5.92 (dd, J = 15.8 and 1.42 Hz, 1 H), 5.54 (m, 1 H), 3.73 (s, 3 H), 3.63 (m, 2 ), 2.08 (s, 3 ), 1.84 (m, 2 ), 0.89 (m, 1 ), 0.86 (d, J = 6.86 Hz, 6 ), 0.82 (s, 6 ), 0.06 (s, 6 H); 13C NMR 170.0 (C), 166.5 (C), 146.0 (CH/CHg), 120.9 (CH/CHg), 70.0 (CH/CHg), 58.3 (CHg), 51.8 (CH/CHg), 38.8 (CHg), 34.2 (CH/CHg), 25.1 (C), 21.0 (CH/CHg), 20.3 (CH/CHg), 18.5 (CH/CHg), -3.4 (CH/CHg), -3.5 (CH/CHg); IR (neat) 1745 (st), 1735 (st), 1665 (md) cm"1; MS (El, 30 eV) m/e (rel intensity) 309 (1), 307 (1), 271 (2), 117 (100); HRMS matched for [M -SiMe3]+ caled for C14Hgg06 271.15453, found 271.15492. Methyl 4-Acetoxy-5-methylhex-2-enoate (7, R1 = i-Pr).…”
Section: Reactions Of Methyl [(( )-4-chlorophenylmentioning
confidence: 99%