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A simple approach to vicinal pyrrolylphosphane aldehydes was developed. The reaction of Alder's dimer 1 with a set of pyrrolylphosphane derivatives—its oxides, sulfides, and selenides—was studied in detail. While Alder's dimer reacted with phosphane oxides and sulfides at the O and S atoms, phosphane selenides 4a–c were found to be suitable for the introduction of the formyl group into the pyrrole ring. The reaction of highly electrophilic Alder's dimer with pyrrolylphosphane selenides proceeded predominantly at the pyrrolyl nuclei, affording the corresponding aldehydes. The phosphoroselenoyl groups of aldehydes 11 were reduced either with Raney Ni or hexamethylphosphorustriamide under mild conditions, affording pyrrolylphosphane aldehydes 12.

A N C3 migration of the dichlorophosphino group has been revealed in the phosphorylation of unsubstituted indole with phosphorus trichloride. Several 3-phosphorylated NH-indole derivatives have thus been obtained and N-acylation of one of the products has been performed. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:235–239, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20540

A successive N C2 C3 migration of the dichlorophosphino group has been found to occur in phosphorylation of unsubstituted pyrrole with phosphorus trichloride. As a result of this migration, a number of hitherto unknown C-phosphorylated N-unsubstituted pyrroles have been obtained. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:671–676, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20495

Isothiocyanatophosphonium salts bearing an aroxy group at the phosphorus atom have been obtained for the first time. As found, these compounds undergo an intramolecular heterocyclization to give hitherto unknown benzoxazaphosphininethiones or cyanoiminophosphoranes, according to the nature of the substituents on the aryl ring. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:667–670, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20491

Phosphorylation of N-trimethylsilyl- and N-dimethyl-tert-butylsilylpyrroles with phosphorus tribromide in pyridine proceeds selectively at position 3 of the pyrrole ring. Removal of the trialkylsilyl protecting group has furnished the first representatives of N-unsubstituted 3-phosphorylated pyrroles. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:93–96, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20416

The investigation concerns the effect of a bulky substituent at the pyrrole nitrogen atom on the orientation and regioselectivity of pyrrole phosphorylation with phosphorus(III) halides. As shown, phosphorylation of N-iso-propylpyrrole with phosphorus tribromide or trichloride proceeds nonregioselectively at positions 2 and 3 but it is followed by the 2 3 migration of the dihalogenophosphine group which quantitatively yields the 3-isomer. N-tert-butylpyrrole is regioselectively phosphorylated with halogenophosphines at position 3. The tert-butyl substituent at the nitrogen atom does not preclude the binding of even two or three pyrrolyl residues to the phosphorus atom. The key compounds, 3-pyrrolyldihalogenophosphines, were isolated in a pure state, characterized and used to obtain a number of stable phosphorus(V) derivatives. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:599–604, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20158

Pyrroles, indoles, indolizines, and 2-methylfuran are vigorously C-acylated with isocyanatophosphoryl dichloride. The resulting heteroaryl-substituted isocyanatophosphoryl dichlorides provide a convenient access to a variety of products.© 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 343–348, 1999

Pyrroles, indoles, indolizines, and 2-methylfuran are vigorously C-acylated with isocyanatophosphoryl dichloride. The resulting heteroaryl-substituted isocyanatophosphoryl dichlorides provide a convenient access to a variety of products.© 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 343–348, 1999

Isothiocyanatophosphonium salts bearing an aroxy group at the phosphorus atom have been obtained for the first time. As found, these compounds undergo an intramolecular heterocyclization to give hitherto unknown benzoxazaphosphininethiones or cyanoiminophosphoranes, according to the nature of the substituents on the aryl ring. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:667–670, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20491

A successive N C2 C3 migration of the dichlorophosphino group has been found to occur in phosphorylation of unsubstituted pyrrole with phosphorus trichloride. As a result of this migration, a number of hitherto unknown C-phosphorylated N-unsubstituted pyrroles have been obtained. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:671–676, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20495

A reaction of cyclohexanone phenylhydrazone with (het)aryldihalogenophosphines has been studied. As shown, cyclohexanone phenylhydrazone reacts with phenyldibromophosphine and 5-methyl-2-furyldibromophosphine to provide the corresponding 1,2,3-diazaphospholines in high yields. The diazaphospholines thus obtained have been derivatized. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:81–83, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20074

A new synthetic method is developed which enables a direct one-step introduction of a cyano group into electron-rich heterocyclic systems of the indole, pyrrole, and indolizine series, and also to enamines using isocyanatophosphoryl dichloride.