Synthesis of vinyl sulfones. 23. Addition of organometallic reagents to cyclooctenyl phenyl sulfones

Hardinger, S. A.; Fuchs, P. L.

doi:10.1021/jo00389a019

Cited by 49 publications

(17 citation statements)

References 2 publications

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“…(1R *,2S*,3S *)-1 -(Carbamoyloxy )-2,3-epoxycyclohexane (8): mp 132-133 °C; NMR 3.32 (br s, 2 , 2-H and 3-H), 4.92 (m, W/2 = 22 Hz, 2 , NH2), 5.05 (m, W/2 = 18 Hz, 1 , 1-H).…”

Section: Methodsmentioning

confidence: 99%

Steric control of epoxidation by carbamate and amide groups. Evidence for the carbonyl-directed epoxidation

Kočovský¹,

Starý²

1990

J. Org. Chem.

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61.2 mmol of Me3N in 180 mL of H 2 0 was heated a t 100 "C for 20 h with an initial pressure (room temperature) of 15.7 atm of N2, 29.3 atm of 02, and 208.8 atm of Ar. Samples of the head gas were taken before and after the reaction and were analyzed by mass spectroscopy. The analyses of 0, and N, were also confirmed by GC on a 10 ft molecular sieve column. N2 was added as an internal standard for the analysis of 0, by G.C. The results are shown in the table below. 0 2 N2 Ar COz H2 before reactiono 9.6 (f0.3) 6.6 (*0.4) 82.6 (*0.8) 0 <0.02 after reaction 5.5 (i0.3) 7.3 (f0.4) 87.0 (*0.8) 0.011 0.1 "The balance is Me3N.The organic products were determined by l3C{lH\ NMR spectroscopy. The IR spectra of the head gas also indicate the absence of N,O, NO, and NO,.Deoxygenation of Me3N0. A preliminary experiment indicates that no reaction occurs if an aqueous solution of Me3N0 (0.5 M) is heated first a t 100 "C for 19 h and then at 150 "C for 5 h under 500 psi of argon atmosphere.An aqueous solution of 0.92 M Me3N0 (160 mL) was heated a t 200 "C and 500 psi of argon atmosphere. Samples were taken and analyzed by 13C(1HJ NMR spectroscopy. Me3N0 disappeared with a half-life of 2.5 h; Me3N accounted for about half of the product. At the end of the reaction, CO,, but not 02, was found in the sample of the head gas.Allylic and homoallylic carbamoyloxy groups show a pronounced syn stereodirecting effect on peroxy acid epoxidation similar to that of hydroxy groups (5 -8). Carbonyl oxygen of the ambident carbamoyloxy group has been found to be responsible for this steering. A similar effect operates in olefinic amides (64 -66).

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“…(1R *,2S*,3S *)-1 -(Carbamoyloxy )-2,3-epoxycyclohexane (8): mp 132-133 °C; NMR 3.32 (br s, 2 , 2-H and 3-H), 4.92 (m, W/2 = 22 Hz, 2 , NH2), 5.05 (m, W/2 = 18 Hz, 1 , 1-H).…”

Section: Methodsmentioning

confidence: 99%

Steric control of epoxidation by carbamate and amide groups. Evidence for the carbonyl-directed epoxidation

Kočovský¹,

Starý²

1990

J. Org. Chem.

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“…Stabilizing hydrogen‐bonding interactions between a −OH substituent on the alkene and the peracid oxygen atoms favor epoxidation syn to allylic and homoallylic alcohols 3. A variety of other groups, such as, carboxamides,4 sulfonamides,5 carbamates,6 amido,7 urethano,8 ureido,9 unsaturated acetals,10 sulfones,11 sulfoxides,12 phosphorus oxides,13 and ammonium salts14 have all been reported to show similar syn ‐directing effects. These observations have been associated with hydrogen bonding involving the alkene substituent and the peracid.…”

Section: Methodsmentioning

confidence: 99%

CH⋅⋅⋅O Hydrogen Bonding Influences π-Facial Stereoselective Epoxidations We are grateful to the National Institute of General Medical Sciences, National Institutes of Health (GM-36700) for financial support of this research and the National Computational Science Alliance (Illinois) for computer time and support.

Washington

Houk²

2001

Angew. Chem. Int. Ed.

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“…(25) experiments. In the cases where an AFT spectrum was obtained, the chemical shifts are denoted as "em (no or two attached protons) or "on (one or three attached protons) (26).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of cedranoid sesquiterpenes. V. The biotols

Yates¹,

Grewal²,

Hayes³

et al. 1988

Can. J. Chem.

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. 66, 2805 (1988).Reduction of dimethyl 3-hydroxy-4,4,8-trimethyl-6-oxo-cis-bicyclo[3.3.0]octa-2,7-diene-1,2-dicarboxylate (8) with lithium and ammonia gives dimethyl 3-hydroxy-4,4,exo-8-trimethyl-6-oxo-cis-bicyclo[3.3.O]oct-2-ene-l,2-dicarboxylate (9), which on acetylation, reduction with sodium borohydride, and methanolysis gives dimethyl 3,exo-6-dihydroxy-4,4,exo-8-trimethylcis-bicyclo[3.3.0]oct-2-ene-1,2-dicarboxylate (12). This on 2-decarbomethoxylation followed by treatment with lithium acetylide in the presence of cerium trichloride gives methyl 3-ethynyl-3,exo-6-dihydroxy-4,4,exo-8-trimethyl-cisbicyclo[3.3.0]octane-1-carboxylate (21), which on hydration, diacetylation, and treatment with tri-n-butyltin hydride and azoisobutyronitrile is converted to methyl exo-6-acetoxy-3-acetyl-4,4,exo-8-trimethyl-cis-bicyclo[3.3.O]octane-l-carboxylate (31). Methanolysis of 31. tert-butyldimethylsilylation, and reaction with potassium tert-butoxide in tert-butyl alcohol gives exo-4-tert-butyldimethylsilyloxy-exo-2,6,6-tmthyl[5.3.l~~~]undecane-8,10-dione (35). This on treatment with lithium aluminum hydride followed by oxidation and hydrogenation provides the corresponding 10-deoxo compound, 39. Reaction of this with methyllithium, dehydration, and desilylation with hydrogen fluoride in acetonitrile gives a mixture of (5) Introduction a-Biotol (1) and P-biotol (2), the exo-4-hydroxy derivatives of the prototypical cedranoid sesquiterpenes, a-cedrene (3) and P-cedrene (4), respectively (3), were isolated in 1968 from the alcoholic portion of the essential oil of the wood of Biota orientalis (4). These alcohols are minor components of the oil, cedrol (5) being one of the major components. Their gross structures were assigned on the basis of chemical and spectroscopic methods (4). To establish the relative stereochemistry at C-4, a-biotone (6), formed by oxidation of 1, was reduced with sodium borohydride to a mixture of 1 and 4-epi-a-biotol (7).

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Synthesis of vinyl sulfones. 23. Addition of organometallic reagents to cyclooctenyl phenyl sulfones

Cited by 49 publications

References 2 publications

Steric control of epoxidation by carbamate and amide groups. Evidence for the carbonyl-directed epoxidation

Steric control of epoxidation by carbamate and amide groups. Evidence for the carbonyl-directed epoxidation

Synthesis of cedranoid sesquiterpenes. V. The biotols

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