Exploring allene chemistry using phosphorus-based allenes as scaffolds

• Published in: Pure and applied chemistry Vol. 89; no. 3; pp. 367 - 377
• Main Authors: Swamy, K. C. Kumara, Anitha, Mandala, Gangadhararao, G., Rama Suresh, R.
• Format: Journal Article
• Language: English
• Published: Berlin De Gruyter 01.03.2017; Walter de Gruyter GmbH
• Subjects: Alcohols; Allene; allenylphosphine oxide; allenylphosphonate; benzofuran; Carboxylic acids; Chemical reactions; chromene; Crystallization; cyclization; Cycloaddition; ICPC-21; indolinone; Naphthol; Organic chemistry; Organic compounds; Phosphorus; quinoline; Stoichiometry; Substitutes; Substrates
• ISSN: 0033-4545; 1365-3075
• DOI: 10.1515/pac-2016-0907

In this paper, we review some of our results on cycloaddition and cyclization reactions of allenylphosphonates/and allenyl phosphine oxides. Thus nitro-substituted propargylic alcohols react with P(III)–Cl substrates to lead to unprecedented phosphono-benzazepines or -hydroxyindolinones. A similar reaction using a higher stoichiometry of P(III)–Cl precursor has led to the first observation of spontaneous resolution by crystallization in allene chemistry. In the reaction of these phosphorus based allenes with diphenyl isobenzofuran (DPBF), depending on the substituents, both [α, β] and [β, γ]-cycloaddition products are formed. Extension of this work to sulfur based allenes and leading to a new [4+2] cycloadduct with DPBF is reported. A novel cyclization reaction of a functionalized allenylphosphine oxide with diethylamine leading to 3-diethylamino-4-diphenylphosphinoyl-1-naphthol is discovered. Base-catalyzed reactions of allenylphosphonates with 2-substituted benzaldehdes lead to novel thiochromans, chromenes, and quinolines. Allenylphosphonates undergo phosphonylation in the presence of tetrabutyl ammonium fluoride (TBAF). Vinyl azides derived from allenylphosphonates undergo thermolysis to form bis-phosphonopyrazines. [Pd]-catalyzed reactions of allenes with 2-iodophenols, 2-iodobenzyl alcohol and 3-iodo-indole-2-carboxylic acids lead to a variety of benzofurans, benzopyrans and benzopyranones, respectively.