Synthesis of New Functionalized Heterocyclic [4,3,3] Propellanes via Three‐component Reaction Based on Ninhydrin–Phenol Adducts

Abstract

Three‐component reaction between ninhydrin–phenol adducts, dialkyl acetylenedicarboxylates, and triphenylphosphine was investigated. Utilizing this protocol, dialkyl 10‐oxo‐10H‐4b,9b‐(epoxyethanooxy)indeno[1,2‐b]benzofuran‐12,13‐dicarboxylates as functionalized heterocyclic [4,3,3] propellanes was synthesized in 6‐endo‐trig cyclization mode. 8‐hydroxyquinoline showed serendipitous reactivity and produced para substituted adduct in the reaction with ninhydrin in acetic acid media and hence produced dialkyl 8a‐(4‐(alkoxycarbonyl)‐2‐oxo‐2H‐pyrano[3,2‐h]quinolin‐6‐yl)‐8‐oxo‐8,8a‐dihydro‐2H‐indeno[2,1‐b]furan‐2,3‐dicarboxylate in the reaction with dialkyl acetylenedicarboxylates and PPh3.

Ninhydrin Adducts as Valid Synthon in Organic Synthesis: A Review

“…Sirouspour and Souri reported a fascinating reaction of ninhydrin‐phenol adducts 4 and dialkyl acetylenedicarboxylate 13 in the presence of PPh 3 to obtain propellane derivatives 14 (Scheme ) . Mechanistically it was conceivable that the initial formation of 1,3‐dipolar intermediate A (from PPh 3 and acetylenic compound 13 ) followed by protonation resulted vinyl phosphonium cation B .…”

Chemo‐ and diastereoselective synthesis of new oxa[3.3.3]propellane via a domino cascade four‐component reaction based on diketene

“…[20b] Furthermore, dialkyl 10oxo-10H-4b,9b-(epoxyethanooxy)indeno [1,2-b]benzofuran-12,13-dicarboxylates as functionalized heterocyclic [4,3,3] propellanes were constructed in 2016 by Sirouspour and co-workers from the three-component reaction of ninhydrin-phenol adducts, dialkyl acetylenedicarboxylates, and triphenylphosphine via 6-endo-trig cyclization route. [23] In addition, various furoimidazo [3.3.3]propellanes were formed through reactions of thiocarbonohydrazides and (1,3-dioxo-2,3-dihydro-1H-in-den-2-ylidene)propanedinitrile in tetrahydrofuran. [24] In continuation of our interest in the development of newsynthetic procedures in heterocyclic chemistry, [25] particularly those which are provided through multicomponent reaction [24,26] and especially using diketene as one of the vital component [27] herein, we wish to describe a one-pot, multi-component, metal-free, chemo and diastereoselective synthesis of oxa [3.3.3]propellane derivatives via one-pot four-component reaction in the presence of Et 3 N at room temperature in EtOH.…”

“…[ 20b ] Furthermore, dialkyl 10‐oxo‐10 H ‐4 b ,9b‐(epoxyethanooxy)indeno[1,2‐ b ]benzofuran‐12,13‐dicarboxylates as functionalized heterocyclic[4,3,3]propellanes were constructed in 2016 by Sirouspour and co‐workers from the three‐component reaction of ninhydrin‐phenol adducts, dialkyl acetylenedicarboxylates, and triphenylphosphine via 6‐ endo ‐trig cyclization route. [ 23 ] In addition, various furoimidazo[3.3.3]propellanes were formed through reactions of thiocarbonohydrazides and (1,3‐dioxo‐2,3‐dihydro‐1 H ‐in‐den‐2‐ylidene)propanedinitrile in tetrahydrofuran. [ 24 ]…”