Synthesis of ring D modified morphinan systems via ring expansion of a key codeine intermediate

Ring expansion and ring fragmentation products were synthesized from pentacyclic ketones 3 and 4 via Baeyer-Villiger oxidation. Oxidation of 3 with m-chloroperbenzoic acid afforded delta-lactone 9 which was transformed to enone 12 en route to the C6 inverted ether 14. Analogous oxidation of 4 gave delta-lactone 18. Opening of the lactone ring of 14 and 18 led to seco structures which, in the case of 19, underwent reannulation with incorporation of nitrogen to yield the hydroxylactam 21.     

Catalyst and ring size effects on periselectivity of oxonium ylide rearrangements

Diazoketones were subjected to carbene-transfer with Rh(II) or Cu(II) catalysts to probe the selectivity for rearrangement via five- or six-membered oxonium ylides. 4,5-Bis(benzyloxy) and 4-allyloxy-5-benzyloxy substrates 3a,b showed a large preference for rearrangement via the five-membered ylide under all conditions. However, a sharp divergence was seen with 5-allyloxy-4-benzyloxy substrate 3c, which underwent predominantly a [2,3]-shift to pyran 5c via the six-membered ylide with Cu(II) catalysis and a [1,2]-shift to furan 4c via the five-membered ylide with Rh(II) catalysis.     

The unexpected conversion of a thiophene ring into a pyrrole ring via a putative nitrene intermediate

Triethylphosphite induced reductive cyclisation of 1-(2-nitrophenyl)-3,5-di(2-thienyl)pyrazole 6 afforded the expected 1,3-di(2-thienyl)pyrazolo[1,2-a]benzotriazole 7 (14%) together with an unexpected product which was shown to be a 2-(2-thienyl)pyrazolo[1,5-a]pyrrolo[2,1-c]quinoxaline 8 derivative (27%). A mechanism for the extrusion of sulfur during the transformation of heterocycle 6 into product 8 is proposed.     

The thiolate anion as a nucleophile Part XI. Effect of the size of the nucleophile

The nucleophilic substitution reactions of some simple fluorobenzenes, C₆H_6?xF_x with sodium methanethiolates Na⁺SR^?(R=Et, $\text{i}$-Pr, $\text{t}$-Bu) have been studied. Some fully substituted products, C₆H_6?x(SR)_x, could be obtained in DMF as solvent with R = Et and $\text{i}$-Pr, but not when R = $\text{t}$-Bu. All the new products isolated have been characterized by elemental analysis, and NMR (H-1 and F-19), infrared and mass spectroscopy.     

A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide

The reaction of methyl (diethylphosphoryl)dithioformate (6) with diaryldiazomethanes 7a-d in THF at −60 °C to room temperature followed by desulfurization is shown to be a convenient method for the preparation of 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates 8a-d. The analogous reactions with 2-diazoacenaphthen-1-one (7f) or 2-diazocamphor (7g) in refluxing THF yield selectively the corresponding (Z)- and (E)-vinyl phosphonates 8f and 8g, respectively. These products can be easily oxidized to the vinylsulfoxides 13 and vinylsulfones 14. On the other hand, methyl (diethylphosphoryl)dithioformate (6) and 2-diazo-1,2-diphenylethanone (7e) in boiling THF react to give the 1,3-oxathiole 12. All these reactions occur via an intermediate thiocarbonyl ylide 11 followed by 1,3-dipolar electrocyclization and sulfur extrusion or 1,5-dipolar electrocyclization.     

The ketene thioacetal group as a cationic cyclization terminator. : A synthesis of the pyrrolizidine ring system.

A cationic cyclization to the pyrrolizidine ring system is reported in which a ketene thioacetal group serves as an efficient terminator for 5-membered ring formation. (±)-Supinidine is prepared using this methodology.     

有机碲Ylide反应XII用碲Ylide合成双环丙烷衍生物

由相应的碲盐生成的某些碲ylide, 能顺利地和1, 4-双(3-取代苯基-3-酮-1-丙烯基)苯, 1, 5-二取代苯基-1, 4-戊二烯-3-酮反应生成双环丙烷衍生物, 反应具有高立体选择性, 产率为61.8-88.8%。     

Guanidinium ylide mediated aziridination: identification of a spiro imidazolidine-oxazolidine intermediate

We successfully isolated a spiro imidazolidine-oxazolidine intermediate in the reaction of guanidinium ylide mediated aziridination using alpha-bromocinnamaldehyde. X-ray crystallographic analysis unambiguously revealed that the stereogenic centers of the spiro intermediate were in a trans configuration. The role of the spiro compound as an intermediate in the aziridination reaction was confirmed by observation of its smooth chemical conversion into aziridine products.     

Studies on nucleophilic ring opening of some epoxides in polar protic solvents—I

The epoxides of the type 4 undergo ring-opening with carbanions; without exception, the nucleophiles attack at C-1 in spite of the increased steric hindrance at the site (as in epoxides 4b and 4e having peri-substituents). Interaction of the epoxide 4b with the anion of diethyl methylmalonate in refluxing t-butanol afforded, besides other products, the novel cyclopropane carboxylic acid 12. What is more significant is that although the formation of the trans-lactone on the whole is favoured in the ring opening of epoxides 4, at least in two cases, 4b and 4c, there is considerable formation of cis-lactones, a result that remains unexplained. Attempted synthesis of the model cis-lactone 3c always resulted in the formation of a 1:1 mixture of the cis-3c and the trans-lactone 2a. The stereochemistries of the cis- and the trans-lactones described in this paper have been unambiguously established from the position of the 3a-proton signals of these γ-lactones in their NMR spectra.     

Photochemical reactions. 134th Communication. Photochemistry of 5,6-epoxy-5,6-dihydro-3,4-methano-β-ionone: Influence of a cyclopropane ring on the reactivity of an ylide intermediate

On ¹n,π*-excitation(λ > 347 nm), the diastereomeric methanoepoxyenones (E)- 6 undergo isomerization via C,O-cleavage of the oxirane leading to diastereomeric photoproducts ((E)- 5 →(E/Z)- 13 and 14 ; (E)- 6 →(E/Z)- 16 and 17 ). On ¹π,π*-excitation (λ = 254 nm) of either (E)- 5 ) or (E- 6 the photoproducts 9, 10 and 11 are formed. By laser flash photolysis (λ = 265 nm) the ylide intermediate 3 was detected, with a lifetime of 10 μs in MeCN at ambient temperature. Stern-Volmer analysis of the ylide quenching by MeOH disclosed that compounds 9 and 10 , but not 11 , arise from the ylide intermediate e .     

Photochemical reactions. 146th communication. Photochemistry of conjugated methano-epoxydienes: Participation of the neighboring cyclopropane ring in product formation via carbonyl ylide and carbene intermediates

On singlet excitation (λ = 254 nm, THF, pentane or hexane), the diastereoisomeric methano-epoxydienes (E)- 6 and (E)- 7 undergo interconversion and yield the products 8 – 11 . The main process is the cleavage of the oxirane ring to the vinyl carbene intermediate e which undergoes addition to the adjacent double bond furnishing the cyclopropene 8 . The alternative carbene intermediate f is evidenced by the formation of the cyclobutene 10 . For the fragmentation leading to 11 , the carbene f as well as the dipolar species h are considered as possible intermediates. On triplet sensitization (acetone, λ > 280 nm), (E)- 7 shows behavior typical of epoxydienes, undergoing fission of the C? O bond of the oxirane ring and isomerization to the compounds 13 , 14 and (E/Z)- 15 .     

Enantioselective synthesis of allenic esters via an ylide route

Pseudo-C2-symmetric chiral phosphorus ylides have been designed and synthesized for the enantioselective preparation of allenic esters, and up to 92% ee has been achieved.     

用碲Ylide合成杂环取代环丙烷衍生物

本文报道了由碲盐和杂环取代查尔酮反应合成杂环取代环丙烷衍生物的简便方法。     

Effect of protic cosolvents on the photooxygenation of diethyl sulfide

The sluggish (kr < 10kq) photooxygenation of diethyl sulfide in both benzene and other aprotic solvents such as acetone and acetonitrile is made efficient by addition of small amounts of alcohols and, with a much more conspicuous increase, of phenols and carboxylic acids (<0.1% additive is sufficient in this case). A kinetic analysis shows that the effect is accounted for by interaction of the protic additives with the first formed intermediate, the persulfoxide, in competition with cleavage to the components. The thus obtained rate constants kH linearly correlate with the acid strength of the additives, and the effect is rationalized as a general acid catalysis. Hydrogen bonding of the persulfoxide under this condition accounts in an economic way for the observed data, including co-oxygenation of Ph2SO in mixed solvents.     

Effect of water and protic solvents on polysaccharide-based column efficiency

In the present study, polysaccharide-based columns were used to evaluate the efficiency of columns in response to the introduction of water and protic solvents (methanol and ethanol) into the mobile phase, replacing acetonitrile. While increasing water content frequently enhances enantiomer resolution, the inclusion of water, particularly when combined with methanol and ethanol in the mobile phase, has an adverse impact on mass transfer, thus influencing the column plate height. These effects are more pronounced with ethanol, and in many cases, van Deemter plots exhibit the absence of a minimum point optimal in the explored range. Consequently, acetonitrile and its water mixtures are the preferred choices to mitigate these effects for situations in which the chiral column is operated at a relatively high flow rate (> 1 mL/min in a 4.6 mm column).     

Lewis and protic acid mediated Nicholas reactions of 3-acetoxycyclohept-1-en-4-ynedicobalt hexacarbonyl: site selectivity of nucleophile incorporation

Nicholas reactions on the cation derived from the cyclic allylic acetate alkynedicobalt complex 1 favour the γ-site kinetically for most nucleophiles, with increasing amounts of α-products in cases with greater nucleophilicity. Some regiocontrol in introduction of a specific nucleophilic fragment is possible by using different nucleophiles. Under conditions where reversibility is possible, the thermodynamically favoured site is exclusively γ-.     

Effect of ring size on photoreactivity of medium and large ring esters.

Photochemical studies on 7,8,12,14,16 and 20 membered cyclic esters have been carried out in benzene and methanol. Decar☐ylation and solvolysis ascribable to β- and α-scission respectively are observed in case of seven and eight membered cyclic esters. Larger rings do not undergo these photoreactions thus demonstrating effect of ring size on photoreactivity.