Cycloadducts from Diazocumulenes and 1,2,3(λ3)-Diazaphospholes: Thermolysis Generates Products Derived from 3-Alkenylidene-1,2,3(λ5)-diazaphospholes

Kerth, Jochen; Maas, Gerhard

doi:10.1002/(sici)1099-0690(199910)1999:10<2633::aid-ejoc2633>3.0.co;2-i

Cited by 15 publications

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References 21 publications

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“…16,17 In a similar manner, diazocumulenes 4, co-existing as the minor component in equilibrium with (1-diazo-2-oxoalkyl)silanes 3, 18 underwent [3 2] cycloaddition with 1 (R 2 , R 3 = alkyl, H) at 20°C when R 1 = Ac or Bz, while in the case of R 1 = Me or Ph no reaction took place up to ca 60°C, where thermal dediazoniation of the diazo compound occurred. 19 Furthermore, we found that diazocumulenes 4 undergo 1,3-dipolar cycloaddition…”

Section: Introductionmentioning

confidence: 97%

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Jikyo

Schatz

Maas

2003

J of Physical Organic Chem

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The molecular geometries and the frontier orbital energies of three diazo compounds [diazodiphenylmethane (2), the a-silyl-a-diazoketone 3 and the isomeric 2-siloxy-1-diazoalkene 4], 10 heterophospholes with a P=C bond and two heterophospholes with a P=N bond were obtained from DFT calculations at the B3LYP/6-311G** level. The 1,3-dipolar cycloaddition reactivity of diazo compounds 2-4 toward the heterophospholes is discussed on the basis of FMO theory. It is concluded that in most cases, the dominant frontier orbital interaction is between the HOMO(diazo) and the LUMO(heterophosphole), and that the reactivity should decrease in the order 2 >4 >3. The 1,2-thiaphosphole 9 and 1,3-azaphosphole 10 have HOMOs of high energy and, therefore, the HOMO(heterophosphole)-LUMO(diazo) interaction is also important. Among the different types of heterophospholes considered here, the 2-acyl-1,2,3-diazaphosphole 5, 3H-1,2,3,4-triazaphosphole 8, 1,2-thiaphosphole 9 and 1,3,4-thiazaphosphole 14 are predicted to have the highest dipolarophilic reactivities. These conclusions are in qualitative agreement with available experimental results. epoc across the P=C bond of 1,2,3,4-triazaphospholes 20 and 1,2-thiaphospholes, 21 while some other heterophosphole systems were not suited as dipolarophiles.These few examples suggest that it is desirable to have an estimate of the dipolarophilic reactivity of various types of heterophospholes. Within the theoretical frame-Scheme 1

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Section: Introductionmentioning

confidence: 97%

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Jikyo

Schatz

Maas

2003

J of Physical Organic Chem

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Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

Kerth

Maas

2001

European J Organic Chem

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ChemInform Abstract: Cycloadducts from Diazocumulenes and 1,2,3(λ³)‐Diazaphospholes: Thermolysis Generates Products Derived from 3‐Alkenylidene‐1,2,3(λ⁵)‐diazaphospholes.

Kerth

Maas

2000

ChemInform

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Cycloadducts from Diazocumulenes and 1,2,3(λ3)-Diazaphospholes: Thermolysis Generates Products Derived from 3-Alkenylidene-1,2,3(λ5)-diazaphospholes

Cited by 15 publications

References 21 publications

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

ChemInform Abstract: Cycloadducts from Diazocumulenes and 1,2,3(λ³)‐Diazaphospholes: Thermolysis Generates Products Derived from 3‐Alkenylidene‐1,2,3(λ⁵)‐diazaphospholes.

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Cycloadducts from Diazocumulenes and 1,2,3(λ3)-Diazaphospholes: Thermolysis Generates Products Derived from 3-Alkenylidene-1,2,3(λ5)-diazaphospholes

Cited by 15 publications

References 21 publications

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Reactivity of heterophospholes toward 1,3‐dipolar cycloaddition of diazo compounds—an FMO analysis

Polycyclic Isophosphindole Derivatives by Intramolecular Trapping of 2‐Phospha‐1,3‐diyls or Isomeric Bis(methylene)phosphoranes

ChemInform Abstract: Cycloadducts from Diazocumulenes and 1,2,3(λ3)‐Diazaphospholes: Thermolysis Generates Products Derived from 3‐Alkenylidene‐1,2,3(λ5)‐diazaphospholes.

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ChemInform Abstract: Cycloadducts from Diazocumulenes and 1,2,3(λ³)‐Diazaphospholes: Thermolysis Generates Products Derived from 3‐Alkenylidene‐1,2,3(λ⁵)‐diazaphospholes.