Rhodium catalyzed hydroformylation of 2-phenylsulfonylbicyclo[2.2.1] alkenes: effect of the phenylsulfonyl group

The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and norbornadiene derivatives catalyzed by the unmodified Rh(CO)₂acac system are presented. The reaction, occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the regioselectivity of the process.     

Synthesis of alkenes from tertiary esters utilizing the triphenylphosphine-iodine system

The treatment of tertiary esters with triphenylphosphine and iodine under mild conditions gives the most stable alkene in good yield. Formates, acetates and trifluoroacetates were studied.     

Absolute Rate Constants for the Addition of the 1‐(tert‐Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution

Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical ^.CHMeCO₂(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain.     

Reactions of Electron-Rich Olefins with Proton-Active Compounds

Proton-active substances react with certain electron-rich olefins with cleavage of the central C?C double bond to give compounds that can be formally regarded as insertion products of nucleophilic carbenes. If they satisfy certain structural conditions, they isomerize with β elimination to give open-chain compounds. Both CH-acidic compounds and compounds containing NH or OH groups can undergo this reaction. The mechanisms are discussed, and the importance of the intermediate products to biochemistry (thiamine, tetrahydrofolic acid) is indicated.     

Gas chromatographic retention indices for alkenes on OV-101 and squalane capillary columns

Summary Gas chromatographic retention indices for 47 C₅ to C₈ alkenes on OV-101 dimethylsilicone at 50 and 70 °C were determined within a standard deviation of 0.3i.u. Data obtained on OV-101 are compared with those measured on squalane. The comparison of the retention index and dl/dT values from both columns is presented as linear regression equations with correlation coefficients greater than 0.98.     

An approach for quinolines via palladium-catalyzed Heck coupling followed by cyclization

2-Iodoaniline reacts with α,β-unsaturated carbonyl compounds in DMF at 100 °C in the presence of a catalytic amount of a palladium catalyst along with a base to afford the corresponding quinolones or quinolines in moderate to good yields.     

Heck arylations of pent-4-enoates or allylmalonate using a palladium/tetraphosphine catalyst

The Heck reaction of aryl halides with functionalised alk-1-enes should be a powerful method for the synthesis of functionalised (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl chain when there are no substituents on the C3 carbon of the alk-1-enes. We observed that for the arylation of ethyl pent-4-enoate, ethyl 2-methylpent-4-enoate or dimethyl allylmalonate this migration could be partially or completely controlled using appropriate reaction conditions. The ramification on the alkyl chain and the substituents on the aryl halide have also an important influence on this migration. Moreover, the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C₃H₅)]₂ system catalyses this reaction with a wide range of aryl bromides using very high ratio substrate/catalyst in good yields.     

羧基膦－钯－酸体系催化烯烃氢酯基化反应

以钯－膦－酸体系催化烯烃氢酯基化的反应日显重要，而膦配体是决定此反应的重要因素，用二苯基膦乙酸（ＤＰＡ）为配体的钯催化剂体系，对烯烃的氢酯基化反应作了研究。对影响反应的各种因素如反应温度、反应压力、不同的溶剂、膦配体及酸助剂的量等作了考察，发现此配体对烯烃的区域选择性有改善。并用此催化体系对不同结构的烯烃进行了研究，发现有如下的活性顺序：环烯烃＞直链端烯＞直链内烯。     

Stereocontrol in Organic Synthesis Using the Diphenylphosphoryl Group

In 1959, Horner showed that metalated alkyldiphenylphosphane oxides react with aldehydes or ketones to give alkenes. With this reaction, the diphenylphosphoryl (Ph₂PO) group made its entrance into synthetic organic chemistry. In the thirty-six years since that date, extensive research has shown that this olefination, the Horner–Wittig reaction, has unique properties that make it much more than simply the phosphane oxide cousin of the more famous phosphorus-based olefinations—the Wittig reaction (based on phosphonium salts) and the Wadsworth–Emmons reaction (based on phosphonate esters). Early work on the Horner–Wittig reaction concentrated on the reactivity of phosphane oxides and the regioselectivity of their reactions, but more recently the power of the Ph₂PO group to control the stereochemistry of alkenes, and to produce “on demand” either stereoisomer in high stereochemical purity, has emerged. From the study of these stereocontrolled Horner–Wittig reactions arose the realization that the Ph₂PO group is useful not only for the control of the two-dimensional stereochemistry of alkenes, but also of three-dimensional stereochemistry in general. After a brief introduction to phosphane oxide chemistry, this review will examine the Horner–Wittig reaction, in both its original and “stereocontrolled” varieties. From there, we will move on to an account of the stereoselective construction of molecules containing the Ph₂PO group, concentrating on the stereochemical directing effects of the Ph₂PO group and on the role of its unique combination of attributes—steric bulk, electronegativity, and Lewis basicity—in controlling these reactions. Finally, we will present what is intended as a practical guide to this chemistry, covering the type of functionalized alkenes that have been made with the help of the Ph₂PO group and giving guidelines that we hope will help the organic chemist to make the most of the chemistry the Ph₂PO group has to offer.     

Behaviour of water-soluble dinuclear rhodium complexes in the hydroformylation reaction of oct-1-ene

The biphasic hydroformylation reaction of oct-1-ene, has been investigated by using the water-soluble dinuclear complex [Rh₂(μ-S^tBu)₂(CO)₂(TPPTS)₂] as precursor. Addition of ethanol as a cosolvent dramatically improved the yields but the good regioselectivity in linear aldehyde observed for neat oct-1-ene—water systems (97%) decreased to 83% (for 22% ethanol w/w). It is shown that the dinuclear framework cannot be maintained, that the mononuclear complex [RhH(CO)(TPPTS)₃] is formed, and that thiol and significant amounts of [Rh₂(μ-S^tBu)₂(CO)₄] move into the organic phase. This reaction from the dinuclear species requires the simultaneous presence of water and carbon monoxide. Introduction of the water-soluble thiol HS(CH₂)₃NMe₂ in the bridging positions affords the complex [Rh₂(μ-S(CH ₂)₃NHMe₂)₂(CO)₂(TPPTS)₂]Cl₂ which can be kept in the aqueous hase but has a low level of catalytic activity.