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1.
Cycloaddition reactions between vinyl ethers 3 and -quinone methides 2, thermally generated from 2-hydroxybenzyl alcohols 1, have been studied. The structure and conformational preferences of the 4-substituted 2-ethoxy-(2,3)-dihydro-2-benzopyrans 4–9 obtained, which show new interesting features, are discussed together with competitive kinetic data. The cycloaddition process is concerted and involves -quinone methides in the -configuration. The OEt- transition state seems to be preferred with ethyl vinyl ether and -1-propenyl ethyl ether, whereas with -1-propenyl ethyl ether the stereoselectivity of the cycloaddition process depends on substituents on the methylene group of the starting alcohol 1. These results are discussed in terms of and preference of the propenyl ether methyl group. 相似文献
2.
Roshantha A.S. Chandraratna Robert R. Birge William H. Okamura 《Tetrahedron letters》1984,25(10):1007-1010
The electronic absorption spectra of the four new 12---locked retinals (1a–1d) bearing 7-, 11- double bond geometries are described and compared with those of analogous 7-, 11--geometries (1e–1h) and parent retinals (2a-h). 相似文献
3.
Lithiation of both ()- and ()-3-trimethylsilyl-2-propenyl ,-diisopropyl carbamate 2 affords the (2) -lithium compound 3. Aluminium- or titanium-mediated addition to aldehydes, 4 gives (1)-(3*4*)-enol carbamates 7. A stereospecific Peterson elimination (borontriflouride- or base-mediated) introduces the second double bond either with (3)- or with (3)-configuration. So just by reagent selection for each of the two steps, (1,3)-, (1,3)-, (1,3)-, or (1,3)- dienes 8 - 11, respectively, are prepared with stereoselectivities up to > 99.7% 相似文献
4.
In addition to already known sesquiterpene aldehydes, the lactaranes piperdial 1 and piperalol 2 were isolated from extracts of , and (larger fungi). 相似文献
5.
By an appropriate choice of cation, three of the four possible aldols from the reactions of the chiral α-silyloxy ketone 1 with aldehydes may be obtained. The , lithium enolate provides 6, the , boron enolate gives 7, and the magnesium enolate affords 8. 相似文献
6.
Methods were developed to prepare 1 -methyl-, 3-methyl- and 4-0-methyl-ψ-isocytidine by selective methylation.35O-Tetraisopropyldisiloxanyl-ψ isocytidine (8) was trimethylsilylated and then treated with MeI and, after deprotection, 1 -methyl-ψ isocytidine (6) was obtained. The 2deoxy analog (7) was also prepared in a similar manner from the 2deoxy analog (10) of 8. Treatment of 8 with CH2N2 afforded the 3-methyl-ψ-isocytidine derivative (19) as the major product. Methylation with diazomethane also occurred mainly on N3 of the 2deoxy analog 10 to form 20. Removal of the 3 5O-protecting group from 19 and 20 afforded 3-methyl-ψ-isocytidine (14) and its 2-deoxy analog (15), respectively. 2-N-Acetyl- 35O-tetraisopropyldisiloxanyl-ψ-isocytidine (24), on the other hand, gave the 4-O-methyl derivative (25) as the major product upon CH2N2 treatment. Subsequent deprotection of 25 afforded 4-O-methyl-ψ-isocytidine (29). aiv51b1p33b 相似文献
7.
The enamino-thione, 1c, reacts with acrylonitrile and 2-chloroacrylonitrile at room temperature to give 3,4-dihydro-4-(1-pyrrolidinyl)-2-thiopyrans, 4 and 5, respectively. The reaction between 1-aryl-3-(1-pyrrolidinyl) (piperidino)-apropene-1-thiones, 1a-c (1d-f), and dimethyl acetylenedicarboxylate gives 4-(1-pyrrolidiny)(piperidino)-4-thiopyrans, 6a-c (6d-f). Compounds 1a-c (1d-f) and ethyl propiolate produce 2-(1-pyrrolidinyl) (piperidino)-2-thiopyrans, 8a-c (8d-f), and a new type of rearrangement is observed. The 2-thiopyran, 9, is formed from 1b and ethyl 3-propiolate, which elucidates the mechanism. 1H and 13C NMR data of 6 and 7 are discussed. 相似文献
8.
9.
Enamino-thiones 1 prepared from the corresponding enaminones by thiation with Lawesson's Reagent, were allowed to react with 2-chloroacrylonitrile and dimethyl acetylenedicarboxylate giving dihydro-2-thiopyrans, 2, and 4-thipyrans, 3, respectively. The reaction of 1a with ethyl propiolate at room temperature afforded 4-thipyrans, 4a, which on standing rearranged to 2-thiopyran, 5a(1, 3 amide shift). The reaction of 1b with ethyl propiolate produced 4b and 5b. Some of the 13C NMR data are reported. 相似文献
10.
A stereoselectivity in an intramolecular cycloaddition of the olefinic -quinodimethanes 13 and 23 generated from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)--4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described. 相似文献
11.
The geometry and the relative stability of bicyclic compounds 1–20 have been calculated by standard quantum mechanics methods.MINDO/3 yields the following stability order of isomeric norbornyl cations (relative energies in ): 1-norbornyl cation 9 (0.0); 1.7 σ-bridged cation 6 (0.7); 7-norbornyl cation (nonplanar) 7 (1.1); 2-norbornyl cation (classical) 2 (4.2); 7-norbornyl cation (planar) 8 (4.3); 2-norbornyl cation (bridged) 1 (6.1). The stability of the same ions calculated by ab initio methods (STO-3G, MINDO/3-geometry) leads to an order more nearly consistent with experimental results: 2-norbornyl cation (classical) 2 (0.0); 2-norbornyl cation (bridged) 1 (5.9); 7-norbornyl cation (planar) 8 (11.1); 1-norbornyl cation 9 (14.6); 7-norbornyl cation (nonplanar) 7 (21.2). For the secondary 7-norbornyl cation, MINDO/3 gives a pyramidal configuration, 3.2 more stable than the planar form. In contrast, the ab initio results (complete optimization of all geometrical parameters) indicate the planar cation to be the most stable form. The bridged structure of 2-norbornyl cation 1 is calculated (STO-3G, partly optimized) to be 4.3 less stable than the classical counterpart, 2. For the lower homologues 12 and 13 (STO-3G, complete geometry optimization), this difference is 6.4 . However, more extended basis sets should favour the bridged structures. The hydrogen bridged norbornyl cations 3, 4, and 5 have been calculated (STO-3G, partly optimized) to be 14.4, 23.6 and 29.9 less stable than 2. The stability differences between the corresponding tertiary bicyclic ions 10 vs 11, and 14 vs 15 are calculated (ab initio) to be 15.3 and 19.0 kcal/mole, respectively, in favour of classical structures. The influence of methyl substitution at positions C1 and C6 (exo) on bridged and unbridged structure of 2-norbornyl cation is calculated. Pyramidal secondary and tertiary 2-norbornyl cations 19 (a; R=H, b; R=CH3) and 20 (a; R=H, b; r=CH3) have been used to model the electrical effects in the solvolysis transition states of epimeric 2-norbornyl esters. Due to more efficient hyperconjugation the pyramidal exo cation is stabilized more than the endo cation by 5.2 for the secondary series and 3.5 for the tertiary series. Bonding of endo cation 20 with a nucleophile should be stronger than bonding of exo cation 19 due to more efficient HOMO-LUMO interaction. 相似文献
12.
2-Hydroxybenzoic acid heated with 2,4 - bis(4 - methoxyphenyl) - 1,3,2,4 - dithiadiphosphetane - 2,4 -disulfide, 1, gave 2 - (p - methoxyphenyl) - 4 - 1,3,2 - benzoxathiaphosphorin - 4 - one 2 - sulfide, 3, and its thio-analogue, 4, while its ethyl or phenyl esters gave 4 as the sole product. 2 - Mercaptobenzoic acid and its ethyl ester when heated with 1 produced 3 - 1,2 - benzodithiole - 3 - one, 8, 3 -1,2 - benzodithiole - 3 - thione, 9, and 2- (p - methoxyphenyl) - 4 - 1,3,2 - benzodithia - phosphorin - 4 - one 2 - sulfide, 10. The reaction of 2 -aminobenzoic acid with 1 gave 1,2 - dihydro - 2 - (p - methoxyphenyl) - 4 - 3,1,2 - benzoxaphosphorin - 4 - one 2 - sulfide, 12. Reactions of 1 with methyl 2 - aminobenzoate and 2 - aminobenzamides are described. Mechanistic considerations for the formation of the heterocyclic phosphorus compounds are presented. 相似文献
13.
14.
The indolization of deoxybenzoin ,, (Me, MeO, Cl), -NO2 and -EtO-phenylhydrazones (1) by the above reaction has been examined. All the reactions are carried out at room temperature and high yields of the corresponding indoles (2) are obtained even when -NO2 substituent is present. In this case longer reaction time is necessary. Alkoxyphenylhydrazones give the corresponding indoles (2) in high yields without showing collateral reactions which indeed are present in several Fischer routes on these derivatives. -Substituted phenylhydrazones (1) give a mixture of 4- and 6-substituted indoles in which the 6-isomer is always prevalent, a feature not inherent in the Fischer reactions. The regioselectivity is enhanced by the substituent steric hindrance increasing. The reaction can be also carried out at 0°C with a further improvement of its regioselectivity. 相似文献
15.
Jean-Paul Behr Cynthia J. Burrows Richard Heng Jean-Marie Lehn 《Tetrahedron letters》1985,26(2):215-218
A pathway yielding both and -functionalized macrocycles derived from bis-tartaro-18-crown-6 (1) as well as a selective route to compounds have been developed and applied to the synthesis of new macrobicyclic polyether cryptands (2) and (3), which may also be obtained by direct bridging of the dianhydride (4). 相似文献
16.
trans-7α-carbomethoxy-decal-1-one (2) yields a mixture of the two oxy-esters 6 and 7 on reacting with MeMgX. Ratios were measured for reactions performed in benzene (with X = I) and in THF (with X = Cl). The small variations of the ratios as compared to those obtained in analogous experiments performed with methyl (2-oxo-cyclohexyl)-propionate 4 and methyl 4-methyl-5-oxo-hexanoate 5 suggest that conformational mobility plays a fundamental role in determining the variations of stereospecificity with varying the reaction conditions. Competitive Grignard reactions among 2,4 and 5 show that their reactivities are in the order 4>2>5 ( = 1.7; =0.8) when reactions are performed in benzene with X I and 2>4>5 (= 0.56; =0.25) when reactions are performed in THF with X C1. The experimental data are interpreted in terms of anchimeric assistance given by the ester group to the reactions of the keto group in conformationally mobile δ-keto esters. The occurrence of this effect depends on the reaction conditions which can favour, or not, folded transition states. 相似文献
17.
6,7-Dimethoxy-2-phenyl-4-1,3-benzothiazine (1) and 6,7-dimethoxy-4-phenyl-2-1,3-benzothiazine (2) react with substituted acetyl chlorides to give linearly, and new angularly condensed β-lactam derivatives (4,5). Heating of the latter compounds with hydrogen chloride in anhydrous ethanol leads to the formation of the corresponding 4- and 2-1,3-benzothiazinium chloride, respectively. The configurations of these compounds (the mutual positions of the substituents relative to the β-lactam ring) were determined by 1H and 13C studies, also making use of the aromatic solvent-induced shifts. 相似文献
18.
Photolysis of the N-[ω-(cycloalken-1-yl)alkyl]phthalimides 6b- in each case gave a pair of stereoisomers of spiro-nitrogen multicyclic systems (9b-) in moderate yields, whose stereochemistry was determined by means of chemical and spectroscopic analyses. Similarly, in N-[ω-(inden-3-yl)alkyl]-phthalimides (8), spiro-nitrogen macrocycles up to 13-membered 13a- were obtained in good yields 相似文献
19.
The first asymmetric total synthesis of stoechospermol, a representative spatane diterpene having , , -tricyclo[5.3.0.02,6]decane ring system, was achieved. Using the intramolecular asymmetric (2+2) photocycloaddition reaction of the diastereomeric ester 11, the readily available butenolide 9 was transformed into the optically active dilactone 12a and 12b. Subsequent construction of tricyclic carbon ring system and introduction of substituents in a right stereochemistry gave rise to optically pure stoechospermol 1. 相似文献
20.
The kinetics of the homopolymerizations of styrene, N-(3-dimethylaminophenyl) maleimide (I) and N-(3-dimethylamino-6-methylphenyl) maleimide (II) in benzene and dimethylformamide, and the molecular weights of the polymers were studied. N-(3-Dimethylaminophenyl) succinimide, regarded as a model for polymer I, did not affect the polymerization of styrene. The data indicate degradative transfer of polymer radicals to dimethylformamide and pronounced transfer to monomers I and II (CM ≈ 0.06–0.07). The value of for II is 0.09 . 相似文献