Phosphaalkynes: new building blocks in synthetic chemistry

Regitz, Manfred

doi:10.1021/cr00099a007

Cited by 322 publications

(134 citation statements)

References 55 publications

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“…It was observed 27 that diazoalkanes undergo w x regiospecific 3 q 2 cycloaddition reactions of the type shown in Scheme 1 with alkyl-substituted phosphaalkynes. This is also the normal cycloaddition in the sense discussed previously.…”

Section: Resultsmentioning

confidence: 99%

Approach to regiochemistry using local softness in 1,3-dipolar cycloadditions

Chandra

Nguyen

1998

J. Comput. Chem.

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The principle of hard and soft acids and bases is applied in the local sense to rationalize the regiochemistry in the cycloaddition reactions of a few typical 1,3-dipoles, in particular those with phosphorus-containing dipolarophiles. Local softnesses are calculated using density functional theory. It is observed that the regioselectivity can be explained using these new reactivity descriptors based solely on the properties of the reactants.

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Section: Resultsmentioning

confidence: 99%

Approach to regiochemistry using local softness in 1,3-dipolar cycloadditions

Chandra

Nguyen

1998

J. Comput. Chem.

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“…The nitrile sulphides have been shown to readily decomThe 1,3-dipole cycloaddition reaction is an important synthetic route to a number of heterocyclic systems (1, 2). The nitrile sulphides 1 are a family of 1,3-dipoles that contain a sulphur-nitrogen .rr bond and have been the subject of several recent reviews (3,4).…”

Section: Introductionmentioning

confidence: 99%

The selective complexation of adamantane nitriles by tungsten pentacarbonyl

Jefford¹,

Schriver²,

Zaworotko³

1996

Can. J. Chem.

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Adamantyl-l,3,4-oxathiazol-2-one is usually prepared as a mixture with 1 -adamantanecarbonitrile. To separate these two compounds the mixture is reacted with thf.W(CO),, which selectively forms a complex with the nitrile. The resulting mixture can then be readily separated into pure compounds by sublimation. Characterization data are presented, including the X-ray crystal structure of the nitrile complex, which can be prepared directly from the reaction of the adamantyl nitrile and thf.W(CO),. (Crystal data for C16H,,N05W: orthorhombic, space group Prncn, a = 10.5869(19) A, b = 14.0622(22) A, c = 23.342(4) A, V = 3475.0(11) A' , Z = 8, K = 0.042.) The nitrile can be recovered from the complex by reaction with P(C6H,), followed with separation by sublimation. The reaction of the related 1-cyano-3-(1,3,4-oxathiazo1-2-on-5-y1)-adamantane with thf.W(CO), yields a complex in which the site of coordination is shown spectroscopically to be the nitrile moiety. Semi-empirical calculations at the PM3 level indicate that the oxathiazolone heterocycle may be a poor ligand due to the influence of the exo-and endo-cyclic oxygen atoms.Key words: oxathiazolone, nitrile, tungsten, complexation, selectivity, adamantane.Resume : L'adamantyl-l,3,4-oxathiazol-2-one est gkntralement prkpar6.e sous la forme d'un melange avec l'adamantane-lcarbonitrile. Pour stparer ces deux composts, on fait rtagir le mtlange avec du thf.W(CO), qui forme sklectivement un complexe avec le nitrile. Le mtlange qui en rksulte peut alors &tre sCpark facilement en composCs purs par sublimation. On prCsente des donnCes de caractkrisation, y compris la structure cristalline par diffraction des rayons X du complexe avec le nitrile qui peut &tre prCparC directement par rkaction de l'adamantylnitrile avec du thf.W(CO),. Les donnkes cristallines pour Cl,Hl,NO,W : orthorhombique, groupe d'espace Pmcn, a = 10,5869(19), b = 14,0622 (22)

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“…The 1,3-dipole cycloaddition reaction has been used in recent years in the preparation of a number of new heterocyclic systems (2,3). In these reactions, molecules that incorporate n bonds to the pnictogens and chalcogens have acted as both the dipole and the dipolarophile.…”

Section: Introductionmentioning

confidence: 99%

“…or cage hydrocarbons (such as adamantyl, -C,,H,,) (2). Nitrile sulphides, or the precursor molecules from which they are generated, that would be stabilised by extreme steric protection or substitution with cage hydrocarbons have not been prepared or generated.…”

Section: Introductionmentioning

confidence: 99%

The preparation of 1,2,3,5-dithiadiazolium chlorides from the reaction of nitrile sulphides with thiazyl chloride

Bridson¹,

Copp²,

Schriver³

et al. 1994

Can. J. Chem.

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. Adamantyl-1,3,4-oxathiazol-2-one has been prepared for the first time and from it 1-adamantyl nitrile sulphide has been generated. Characterisation data are presented, including the X-Ray crystal structure of the oxathiazolone. (Crystal data for C,,H,,NO,S: monoclinic, space group F'2,/c, a = 11.334(2) A, b = 7.344(1) A, c = 14.373(2) A, P = 107.74(1)", V = 1139.5(3) AS, Z = 4, R = 0.042). The planar heterocyclic ring is similar to structures observed in the gas phase for other oxathiazolone derivatives. The nitrile sulphide was reacted with dimethyl-acetylene dicarboxylate in situ to give an isothiazole derivative. On a prtparC l'adamantyl-l,3,4-oxathiazol-2-one pour la premikre fois et on l'a utilise pour gCnCrer la sulfure de l-adamantyl nitrile. On prCsente les donntes ayant semi ?i sa caractCrisation, y compris la structure de l'oxathiazolone determinee par diffraction des rayons X. Les donntes cristallines pour C,,H,,NO,S sont les suivantes: cristaux monocliniques, groupe d'espace [Traduit par la Rtdaction]

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Phosphaalkynes: new building blocks in synthetic chemistry

Cited by 322 publications

References 55 publications

Approach to regiochemistry using local softness in 1,3-dipolar cycloadditions

Approach to regiochemistry using local softness in 1,3-dipolar cycloadditions

The selective complexation of adamantane nitriles by tungsten pentacarbonyl

The preparation of 1,2,3,5-dithiadiazolium chlorides from the reaction of nitrile sulphides with thiazyl chloride

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