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1.
N-Acetyl-, N-[(tert-butoxy)carbonyl](Boc)-, and N-[(benzyloxy)carbonyl](Z)-protected tri-, penta-, and heptapeptide methyl esters, 1 – 8 , with a central aminomalonate (Ama) (allyl, methyl, benzyl, or tert-butyl) or (amino)(cyano)acetate (Aca) residue have been prepared by conventional techniques (Schemes 4 – 6). The new peptides with acidic backbone-bound CH groups can be C-alkylated with primary alkyl, allyl, and benzyl halides, under mildly basic conditions (1 equiv. MeONa or t-BuOK in THF); also, they can be added to Michael acceptors such as acrylates, acrylonitrile, methyl vinyl ketone, or nitrostyrene (catalytic amounts of alkoxide bases in THF) (Schemes 7 – 16). In most cases, the products, 48 – 100 , are formed in excellent yields (average of 77%); one of the epimeric products prevails (2 : 1 to > 20 : 1), and the epimers have been separated, isolated in pure form, and fully characterized (without configurational assignments); addition of the co-solvent 3,4,5,6-tetrahydro-1,3-dimethylpyrimidin-2(1H)-one (DMPU) or of LiBr may improve or even reverse the ratio of epimeric products formed; the heptapeptide derivative 8 had to be solubilized for alkylations in THF by the addition of 30 equiv. of LiBr. Cleavage of the Ama groups (benzyl with H2/Pd-C, t-Bu with HCl/Et2O) gave carboxylate derivatives which are actually peptides containing the alkylated aminomalonic acid, the lower homolog of aspartic acid, as residue in the central position. These acids are quite resistant to decarboxylation which had to be achieved by heating at reflux in THF in the presence of 2 equiv. of LiBr and of catalytic amounts of pyridine (Schemes 17 and 18). A one-step removal of the allyl aminomalonate group is possible with Pd/PPh3/formate (Scheme 19). The resulting peptides, 101 – 115 , were formed as separable 1 : 1 mixtures of two epimers. The CN group of the alkylated Aca residue can be removed reductively (Na/NH3; Scheme 20). The value of the new method is compared with that of existing methods of peptide-backbone modification.  相似文献   

2.
Reaction of Di(tert-butyl)- and Diphenyldiazomethane and 1,3-Thiazole-5(4H)-thiones: Isolation and Crystal Structure of the Primary Cycloadduct Reactions of diazo compounds with C?S bonds proceed via the formation of thiocarbonyl ylides, which, under the reaction conditions, undergo either 1,3-dipolar cycloadditions or electrocyclic ring closer to thiiranes (Scheme 1). With the sterically hindered di(tert-butyl)diazomethane ( 2c ), 1,3-thiazole-5(4H)-thiones 1 react to give spirocyclic 2,5-dihydro-1,3,4-thiadiazoles 3 (Scheme 2). These adducts are stable in solution at ?20°, and they could be isolated in crystalline form. The structure of 3c was established by X-ray crystallography. In CDCl3 solution at room temperature, a cycloreversion occurs, and the adducts of type 3 are in an equilibrium with 1 and 2c . In contrast, the reaction of 1 with diphenyldiazomethane ( 2d ) gave spirocyclic thiiranes 4 as the only product in high yield (Scheme 3). The crystal structure of 4b was also determined by X-ray analysis. The desulfurization of compounds 4 to 4,5-dihydro-5-(diphenylmethylidene)-1,3-thiazoles 5 was achieved by treating 4 with triphenylphosphine in boiling THF. The crystal structure of 5f is shown.  相似文献   

3.
(R)-3-Hydroxybutyric acid (from the biopolymer PHB) and pivalaldehyde give the crystalline cis - or (R,R)-2-(tert-butyl)-6-methyl-1,3-dioxan-4-one ( 1a ), the enolate of which is stable at low temperature in THF solution and can be alkylated diastereoselectively ( →3, 4, 5 , and 7 ). Phenylselenation and subsequent elimination give an enantiomerically pure enol acetal 10 of aceto-acetic acid. Some reactions of 10 have been carried out, such as Michael addition (→ 11 ), alkylation on the CH3 substituent (→ 13 ), hydrogenation of the C?C bond (→ 1a ) and photochemical cycloaddition (→ 16 ). The overall reactions are substitutions on the one stereogenic center of the starting β-hydroxy acid without racemization and without using a chiral auxiliary.  相似文献   

4.
The 1,2,3,4-tetrahydro-N-pivaloyl-isoquinoline-3-carboxylic acids 1d , 2d , and 3d , derived from (R)- or (S)-phenylalanine, (S)-dopa, and (S)-α-methyldopa, respectively, are doubly deprotonated with (tert-butyl)lithium in THF and alkylated at the 1-position (products 5 – 10 ). The major diastereoisomers formed are the result of electrophilic attack from the face opposite to the carboxylate group (rel. topicity ul-1,3). Even the addition to benzaldehyd (→ 7,8 ) is highly stereoselective (one of four diastereoisomers is formed exclusively (300-MHz 1H-NMR analysis)), if MgBr2 etherate is added prior to the electrophile. Some of the obtained amino-acid derivatives are decarboxylated by anodic oxidation in MeOH (→ 11 , 12 , 17 ) and NaBH3CN reduction, and converted to the known 1-methyl- and 1-benzyltetrahydroisoquinolines ( 15 , 16 ) of > 95% ee as well as to the phthalide isoquinoline alkaloid (+)-corlumine of ≥80% ee. The synthetic approach described here is compared with other methods of synthesizing enantiomerically pure 1-substituted tetrahydroisoquinolines (and thus an important group of alkaloids, Scheme 1).  相似文献   

5.
Ethyl (1R, 2S)-2-hydroxycyclopentanecarboxylate and -cyclohexanecarboxylate ( 1a and 2a , respectively) obtained in 40 and 70% yield by reduction of 3-oxocyclopentanecarboxylate and cyclohexanecarboxylate, respectively (Scheme 2), with non-fermenting yeast, are converted to bicyclic dioxanone derivatives 3 and 4 with formaldehyde, isobutyraldehyde, and pivalaldehyde (Scheme 3). The Li-enolates of these dioxanones are alkylated (→ 5a – 5i , 5j , 6a – 6g ), hydroxyalkylated (→ 51, m, 6d, e ), acylated (→ 5k, 6c ) and phenylselenenylated (→ 7 – 9 ) with usually high yields and excellent diastereoselectivities (Scheme 3, Tables and 2). All the major isomers formed under kinetic control are shown to have cis-fused bicyclic structures. Oxidation of the seleno compounds 7–9 leads to α, β-unsaturated carbonyl derivatives 10 – 13 (Scheme 3) of which the products 12a – c with the C?C bond in the carbocyclic ring (exocyclic on the dioxanone ring) are most readily isolated (70–80% from the saturated precursors). Michael addition of Cu(I)-containing reagents to 12a – c and subsequent alkylations afford dioxanones 14a – i and 16a – d with trans-fused cyclohoxane ring (Scheme 4). All enolate alkylations are carried out in the presence of the cyclic urea DMPU as a cosolvent. The configuration of the products is established by NMR measurements and chemical correlation. Some of the products are converted to single isomers of monocyclic hydroxycyclopentane ( 17 – 19 ) and cyclohexane derivatives ( 20 – 23 ; Scheme 5). Possible uses of the described reactions for EPC synthesis are outlined. The observed steric course of the reactions is discussed and compared with that of analogous transformations of monocyclic and acyclic derivatives.  相似文献   

6.
Glycosylsulfenyl snf (Glycosylthio) sulfenyl Halides (Halogeno and Halogenothio 1-Thioglycosides, Resp.): Preparation and Reaction with Alkenes The disulfides 11–17 and 20 were prepared from 7, 9 , and 18 via the dithiocarbonates 8, 10 , and 19 , respectively (Scheme 2). The structure of 11 and of 13 was established by X-ray analysis. Chlorolysis (SO2Cl2) of 11 gave mostly the sulfenyl chloride 24 , characterized as the sulfenamide 26 , a small amount of 21 , characterized as the (glycosylthio)sulfenamide 23 , and the glycosyl chloride 27 (Scheme 3). Bromolysis of 11 followed by treatment of the crude with PhNH2 yielded only 28 . Chlorolysis of the diglycosyl disulfide 13 , however, gave mostly the (glycosylthio)sulfenyl chloride 21 and 27 , besides 24 . Bromolysis of 13 (→ 22 and traces of 25 ) followed by treatment with PhNH2 gave an even higher proportion of 23 . Similarly, 20 led to 29 and hence to 30 . In solution (CH2Cl2), the sulfenyl chloride 24 decomposes faster than the (thio)sulfenyl chloride 21 , and both interconvert. Addition of crude 24 to styrene (?78°) yielded the chloro-sulfide 31 and some 37 , both in low yields. The product of the addition of 24 to l-methylcyclohexene was transformed into the triol 32 . Silyl ethers of allylic alcohols reacted with 24 only at room temperature, yielding, after desilylation, isomer mixtures 33 and 34 , and pure 35 . Much higher yields were achieved for the addition of (thio)sulfenyl halides yielding halogeno-disulfides. Good diastereoselctivites were only obtained with 21 , its cyclohexylidene-protected analogue, and 22 , and this only in the addition to styrene (→ 36, 37, 38 ), to (E)-disubstituted alkenes (→ 46, 48, 49a/b, 50a/b, 53 ), and to trisubstituted alkenes (→ 47, 51, 52, 54, 55 ). Other monosubstituted alkenes (→ 41–45 ) and (Z)-hex-2-ene (→ 49c/d,50c/d ) reacted with low diastereoselectivities. Where structurally possible, a stereospecific trans-addition was observed; regioselectivity was observed in the addition to mono- and trisubstituted alkenes and to derivatives of allyl alcohols. The absolute configuration of the 2-chloro-disulfides was either established by X-ray analysis ( 47a ) or determined by transforming (LiAlH4) the chloro-disulfides into known thiiranes (Scheme 5). Thus, 37, 48 , and the mixture of 49a/b and 50a/b gave the thiiranes 56, 61 , and 64 , respectively, in good-to-acceptable yields (Scheme 5). Harsher conditions transformed 56 into the thiols 57 and 58 . Similarly, 61 gave 62 . The enantiomeric excesses of these thiols were determined by GC analysis of their esters obtained with (?)-camphanoyl chloride. Addition of 21 to {[(E)-hex-2-enyl]oxy}trimethylsilane, followed by LiAlH4 reduction and desilylation, gave the known 66 (63%, e.e. 74%). The diastereoselectivity of the addition of 21 to trans-disubstituted and trisubstituted alkenes is rationalized by assuming a preferred conformation of the (thio)sulfenyl chloride and destabilizing steric interactions with one of the alkene substituents, while the diastereoselectivity of the addition to styrene is explained by postulating a stabilizing interaction between the phenyl ring and the C(1)–S substituent (Fig.4).  相似文献   

7.
Acylnitroso dienophiles 4 reacted instantly with 1-(silyloxy)butadiene 5α and led in good yield to the regioisomeric cycloadducts 6 (major) and 7 (minor; Scheme 2, Table 1). cis-Hydroxylation of these primary cycloadducts with OsO4 (catalyst) occurred stereospecifically and in high yield (→ 8 and 9 , resp.; Scheme 2). It was followed by reductive ring cleavage to give either 1-amino-1-deoxy-DL -erythritol or 4-amino-4-deoxy-DL -erythrose derivatives 10 and 14 , respectively, depending on the nature of the reducing agent (Schemes 3 and 4).  相似文献   

8.
The protected disaccharide 44 , a precursor for the synthesis of allosamidin, was prepared from the glycosyl acceptor 8 and the donors 26–28 , best yields being obtained with the trichloroacetimidate 28 (Scheme 6). Glycosidation of 8 or of 32 by the triacetylated, less reactive donors 38–40 gave the disaccharides 46 and 45 , respectively, in lower yields (Scheme 7). Regioselective glycosidation of the diol 35 by the donors 38–40 gave 42 , the axial, intramolecularly H-bonded OH? C(3) group reacting exclusively (Scheme 5). The glycosyl acceptor 8 was prepared from 9 by reductive opening of the dioxolane ring (Scheme 3). The donors 26–28 were prepared from the same precursor 9 via the hemiacetal 25 . To obtain 9 , the known 10 was de-N-acetylated (→ 18 ), treated with phthalic anhydride (→ 19 ), and benzylated, leading to 9 and 23 (Schemes 2 and 3). Saponification of 23 , followed by acetylation also gave 9 . Depending upon the conditions, acetylation of 19 yielded a mixture of 20 and 21 or exclusively 20 . Deacetylation of 20 led to the hydroxyphthalamide 22 . De-N-acetylation of the 3-O-benzylated β-D -glycosides 11 and 15 , which were both obtained from 10 , was very sluggish and accompanied by partial reduction of the O-allyl to an O-propyl group (Scheme 2). The β-D -glycoside 30 behaved very similarly to 11 and 15 . Reductive ring opening of 31 , derived from 29 , yielded the 3-O-acetylated acceptor 32 , while the analogous reaction of the β-D -anomer 20 was accompanied by a rapid 3-O→4-O acyl migration (→ 34 ; Scheme 4). Reductive ring opening of 21 gave the diol 35 . The triacetylated donors 38–40 were obtained from 20 by debenzylidenation, acetylation (→ 36 ), and deallylation (→ 37 ), followed by either acetylation (→ 38 ), treatment with Me3SiSEt (→ 39 ), or Cl3CCN (→ 40 ).  相似文献   

9.
The reaction of 4,6-bis(tert-butyl)-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole with phenylacetylene follows the mechanism of ipso-substitution of the tert-butyl group that is in para-position relative to the endocyclic O atom of the heterocycle, predominantly yielding 8-(tert-butyl)-2,6-dichloro-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorinine (NMR data). The structure of its hydrolysis product, 8-(tert-butyl)-6-chloro-2-hydroxy-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorinine, was proved by X-ray diffraction analysis.  相似文献   

10.
(R)-5-Bromo-6-(bromomethyl)-2-(tert-butyl)-2H,4H-1,3-dioxin-4-one ( 2 ) derived from (R)-3-hydroxybutanoic acid is used for substitutions and chain elongations at the side-chain C-atom in the 6-position of the heterocycle (→ 3–6 , 10–13 ). Subsequent simultaneous reductive debromination and double-bond hydrogenation (Pd/C,H2)occurs with essentially complete diastereoselectivity (>98% ds), with H transfer from the face opposite to the t-Bu group (→ 15–20 , Table 1). Hydrolytic cleavages of the dioxanones then lead to enantiomerically pure β-hydroxy-acid derivatives (overall self-reproduction of the stereogenic center of 3-hydroxybutanoic acid or alkylation in the 4-position of this acid with preservation of configuration).  相似文献   

11.
Stereocontrolled addition of alk-1-enylmetal reagents to the chiral (alkoxymethyl)-substituted acylsilanes (±)- 6 gave rise to α-silylated allyl alcohols, which were converted to the corresponding acetates or propionates 11–16 (Scheme 2). Deprotonation and silylation with Me3SiCl afforded – in an Ireland ester-enolate-accelerated Claisen rearrangement – stereoselectively αδ-silylated γδ-unsaturated carboxylic acids 18–24 (Scheme 4). The Me3Si groups in α-position to the COOH group of these compounds were removed chemoselectively in presence of the chiral silyl group in δ-position by treatment with Bu4NF · 3 H2O or Et3N · 3 HF (→ 27–32 ; Scheme 5). The reaction sequence allows a novel stereocontrolled access to chiral C-frameworks possessing a vinylsilane moiety with its full reaction potential.  相似文献   

12.
Element-Element Bonds. I. Syntheses and Structure of Tetra(tert-butyl)tetrarsetane and of Tetra(tert-butyl)tetrastibetane Dilithium (tert-butyl)arsenide reacts with (tert-butyl)dichloroarsine to give tetra-(tert-butyl)tetrarsetane 1 ; homologous tetra(tert-butyl)tetrastibetane 2 is formed by reduction of (tert-butyl)dichlorostibane with magnesium. The isotypic compounds 1/2 crystallize in the monoclinic space group P21/c with Z = 4. The dimensions of the unit cells determined at ?45 ± 5°C are: a = 957.4(8)/1 000.2(3); b = 1 399.1(14)/1 423.9(4); c = 1 697.4(9)/1 749.8(7) pm; β = 96.02(6)/96.77(3)°. As shown by low temperature X-ray structure determinations (3 531/3 232 symmetry independent reflections; Rg = 4.0/4.6%) the four membered rings E4 (E = As or Sb) are folded; in all-trans configuration the bulky organic substituents occupy pseudo-equatorial positions. Characteristic averaged bond distances and angles are: E? E 244/282; E? C 202/221 pm; ? E? E? E 86/85° ? E? E? C 101/99°. The dihedral angels of the bisphenoides built up by the atoms of the rings are found to be 139/133°.  相似文献   

13.
Racemic and enantiomerically pure methyl N-(tert-butyl)-N-benzyl- and N-1-(phenylethyl)aziridinecarboxylates are prepared by known methods and converted to phenyl thioesters ( 1 , 2 , 15 , 16 ; Schemes 2 and 3). These are deprotonated with lithium diisopropylamide (LDA) and BuLi (for removal of diisopropylamine) in THF at dry-ice temperature. The resulting lithiated species are surprisingly stable and are deuterated, alkylated (CH3, C2H5, allyl, benzyl), and added to aldehydes and nitroolefins in good yields (50–80 %, 18 examples; Schemes 1 and 4–6). The configurational stability of the lithiated species is studied, and conclusions about their structures are drawn. Thus, a C(α)-lithiated ester (see L , Scheme 9) or an O-lithiated ‘enolate’ (see M ) with pyramidalized C(β)-atom is proposed for the species from levorotatory S-phenyl N-benzylaziridinecarbothioate which does not undergo racemization after 1 h at ?60° (THF solution).  相似文献   

14.
Di(tert-butyl)diazomethane: Thermal Decomposition and One-Electron Redox Reactions. Di(tert-butyl)diazomethane is a potential precursor for the still unknown, presumably sterically overcrowded tetrakis(tert-butyl)ethane and, therefore, re-investigated. Its (Hel) photoelectron spectrum exhibits a low first vertical ionization energy of only 7.45 eV. Based on the ionization pattern, both the thermal decomposition above 600 K under nearly unimolecular conditions as well as the N2 elimination at the surface of contacts, [Nix/C], [Rh4(CO)12/SiO2], [Rhx/SiO2], and [Ag2CO3] are analyzed in a flow-system. Heterogeneously catalyzed, N2 is split off already at room temperature, but in contrast to results for sterically less shielded diazo compounds, no dimer is formed, and only mixtures of known di(tert-butyl)carbene-isomerization products are isolated. Cyclic voltammetry at 233 K using a glassy carbon electrode proves a reversible oxidation followed by N2 elimination at higher temperatures and an irreversible reduction. On chemical oxidation, however, no paramagnetic species can be detected, whereas chemical reduction at a potassium metal mirror in a THF solution containing (2.2.2)cryptand, yields the radical anion characterized by ESR spectroscopy. Without a cation-chelating ligand, the radical anion of a hitherto unknown dimer, ((CH3)3C)2C?N? N?N? N?C(C(CH3)3) 2' ?, is generated, which dissociates at higher temperature, forming ((CH3)3C)2?N2' ?. This one-electron reduction product of di(tert-butyl)diazomethane can also be detected after quickly warming up a solution containing presumably the radical anion of the triphenylphosphane adduct ((CH3)3C)2C?N? N? PPh3' ?. In one of these reduction reactions, a N2 elimination is observed.  相似文献   

15.
The Boc-protected tripeptides Boc-Val-Gly-Leu-OH ( 1 ), Boc-Leu-Sar-Leu-OH ( 2 ), Boc-Leu-Gly-MeLeu-OH ( 3 ), and Boc-Val-BzlGly-Leu-OMe ( 64 ), tetrapeptide Boc-Leu-Gly-Pro-Leu-OH ( 9 ), and pentapeptides Boc-Val-Leu-Gly-Abu-Ile-OH ( 4 ), Boc-Val-Leu-Sar-MeAbu-Ile-OH ( 5 ), Boc-Val-Leu-Gly-MeAbu-Ile-OH ( 6 ), Boc-Val-Leu-BzlGly-BzlAbu-Ile-OH ( 7 ), and Boc-Val-Leu-Gly-BzlAbu-Ile-OH ( 8 ) are prepared by conventional methods (Schemes 4–7) or by direct benzylation of the corresponding precursors (Scheme 8). Polylithiations in THF give up to Li6 derivatives containing glycine, sarcosine or N-benzylglycine Li enolate moieties ( A–H ). The polylithiated systems with a dilithium azadienediolate unit ( C, F–H ) are best generated by treatment with t-BuLi. The yields of alkylation of the glycine or sarcosine residues are up to 90%, with diastereoselectivities from nil to 9:1. Normally, the newly formed stereogenic center has (R)-configuration (i.e. a D -amino-acid residue is incorporated in the peptide chain). Electrophiles which can be employed with the highly reactive azadienediolate moiety are: MeI, EtI, i-PrI, allyl and benzyl bromide, ethyl bromoacetate, CO2, and Me2S2 (Schemes 11–13). No epimerizations of the starting materials (racemization of the amino-acid residues) are observed under the strongly basic conditions. Selected conformations of the peptide precursors, generated by shock-freezing or by very slow cooling from room temperature to ?75° before lithiation, give rise to different stereoselectivities (Scheme 11). The latter and the yields can also be influenced by tempering the lithiated species before (Scheme 9) or after addition of the electrophiles (Scheme 12). Besides the desired products, starting peptides are recovered in the chromatographic purification and isolation procedures (material balance 80–95%). The results described are yet another demonstration that peptides may be backbone-modified through Li enolates, and that whole series of analogous peptide derivatives with various side chains may thus be produced from a given precursor.  相似文献   

16.
Fumaramides 3b and 3c bearing the C2-symmetrical pyrrolidine moieties (2R,5R)-2,5-bis(methoxymethyl)pyrrolidine ( 2b ) or 1,3:4,6-di-O-benzylidene-2,5-dideoxy-2,5-imino-L -idit ( 2c ), respectively, as a chiral auxiliary lead to high diastereoselectivities in radical reactions (‘tin method’;Scheme 1). Removal of the chiral auxiliaries affords the corresponding alkylated fumaric acids Scheme 2. Single-crystal X-ray structures of 3b and 3c support arguments that lead to the model of 1,4-stereoinduction.  相似文献   

17.
Base Catalysed Cyclizations of 2-(2-Propynyl)oxy-benzamide Systems 2-(2-Propynyl)oxy-benzamides were cyclized under base catalysis to 6- or 7-membered ring compounds, depending on the reaction conditions. Treatment of 2-(2-propynyl)oxy-benzamide ( 10 ) with sodium methylsulfinylmethanide (NaMSM) in DMSO gave two isomeric oxazepinons 11 (34%) and 12 (7%), while the transformation with sodium-2-propanolate in 2-propanol afforded the oxazinone 13 (34%) and with lithium cyclohexyl-isopropylamide (Li-CHIP) in N-methylpyrrolidone 11 (48%) exclusively (Scheme 4). N-Methyl-2-(2-propynyl)-oxy-benzamide ( 14 ) behaved similarly. In the reaction of 14 with sodium 2-propanolate in 2-propanol yielding the benzoxazinone 16 , the allenyloxy-benzamide 17 could be isolated as an intermediate (Scheme 5). The N-phenyl-compounds 18 and 22 treated with NaMSM/DMSO were converted to 3-anilino-2-methyl-benzo- and naphtho-pyran-4-ones, respectively (Schemes 6 and 7). The mechanisms for these reactions are discussed (Schemes 8, 9 and 10).  相似文献   

18.
The bicyclic monoselenoacetal 7 , easily obtained from (±)-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 6 ) via a radical addition-acyl migration sequence, was converted to racemic 12-epiprostaglandins 3 and 4 . The key intermediate was the all-cis-formyllactone 2b related to Corey lactone (see 12 ; Scheme 1). The presence of a (tert-butyl)-dimethylsilyl protective group for the 11-OH substituent (prostaglandin numbering) was found to be crucial in avoidingβ -elimination and epimerization during the Wittig-Horner reaction (Scheme 2). Epimerization at C(12) at the formyllactone stage (see 2b ) was also possible and gave the known precursor 1b of naturally occurring prostaglandins and analogs.  相似文献   

19.
Acyl- and Alkylidenephosphines. XXIV. (N,N-Dimethylthiocarbamoyl)trimethylsilyl-phosphines and 1.2-Di(tert-butyl)-3-dimethylamino-1-thio-4-trimethylsilylsulfano-1λ5, 2λ3-diphosphet-3-ene In contrast to bis(trimethylsilyl)phosphines R? P[? Si(CH3)3]2 1 {R ? H3C a ; (H3C)3C b ; H5H6 c ; H11C9 d ; (H3C)3Si e }, the more nucleophilic lithium trimethylsilylphosphides 4 react with N,N-dimethylthiocarbamoyl chloride already at ?78°C to give (N,N-dimethylthiocarbamoyl)trimethylsilylphosphines 2 . Working up the reaction, a dismutation of the mesityl derivative 2d is observed, whereas the tert-butyl compound 2b dissolved in toluene, eliminates dimethyl(trimethylsilyl)amine to form 1,2-di(tert-butyl)-3-dimethylamino-1-thio-4-trimethylsilyl-sulfano- 1λ5, 2λ3-diphosphet-3-ene 6b , nearly quantitatively within several days at +20°C.  相似文献   

20.
The sodium salts of (S)-alanine, (S)-phenylalanine, (S)-valine, and (S)-methionine are condensed with pivalaldehyde to imines 5 . Cyclization by treatment with benzoyl chloride in cold CH2Cl2 gives mainly (4:1 to > 99:1) the (2S,4S)-4-alkyl-3-benzoyl-2-(tert-butyl)-1,3-oxazolidin-5-ones ( 6 ; cis-configuration) in high yields (85–95%). The oxazolidinones 6 and 7 are deprotonated with lithium diethylamide (LDEA) in tetrahydrofuran (THF) and alkylated (Mel, benzyl bromide) or hydroxyalkylated (benzaldehyde) to 4,4-disubstituted oxazolidinones 9 and 10 , respectively, with high diastereoselectivity (9:1 to 50:1; relative topicity ul). Hydrolysis of three of the oxazolidinones to amino acids of known configuration and optical purity indicates that little if any racemization occurs in the process.  相似文献   

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