Unit:
Κατεύθυνση Οργανική Σύνθεση και Εφαρμογές της στη Χημική ΒιομηχανίαLibrary of the School of Science
Supervisors info:
Γεώργιος Χ. Βουγιουκαλάκης, Επίκουρος Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Χριστόφορος Γ. Κόκοτος, Επίκουρος Καθηγητής, Τμήμα Χημείας, ΕΚΠΑ
Βικτωρία Μαγκριώτη, Επίκουρη Καθηγήτρια, Τμήμα Χημείας, ΕΚΠΑ
Original Title:
Αειφόρος κατάλυση σε αντιδράσεις πολλών συστατικών και διαδοχικές αντιδράσεις: Σύνθεση νέων τετρα-υποκατεστημένων προπαργυλαμινών μέσω της σύζευξης ΚΑ2
Translated title:
Sustainable catalysis in multicomponent and domino reactions: Synthesis of new tetrasubstituted propargylamines via the KA2 coupling
Summary:
Propargylamines are a unique class of compounds, serving as versatile synthons for a variety of organic transformations and possessing intrinsic value, due to the bioactive nature of certain members of their diverse family. Consequently, their synthesis has been a topic of intense research, which has given rise to a multitude of catalytic reaction systems proceeding through the C-H activation of terminal alkynes and frequently involving the use of sustainable metals. The subgroup of tetrasubstituted propargylamines can be accessed through the multicomponent coupling between ketones, amines and alkynes (KA2 coupling), which remains relatively unexplored, due to the decreased reactivity of ketimine-derived electrophiles. Herein, the development of a novel, highly efficient and user-friendly catalytic system for the KA2 coupling, based on the environmentally benign, inexpensive and readily available zinc acetate, is described. This system has been designed to adhere to the principles of green chemistry and is employed for the multicomponent assembly of unprecedented, tetrasubstituted propargylamines deriving from structurally diverse, challenging and even biorelevant substrates. Notable features of this work include the demonstration of the enhancing effect that neat conditions can have on catalytic activity, as well as the expedient functionalization of hindered, prochiral cyclohexanones, linear ketones, and interesting molecular scaffolds such as norcamphor and nornicotine. The integration of the KA2 coupling into the zinc catalysis platform renders it a more widely available synthetic tool and opens new avenues for its exploration. Importantly, the implications of these findings with regards to the zinc-mediated synthesis of trisubstituted allenes are also addressed.
Main subject category:
Science
Keywords:
Sustainable metal catalysis, multicomponent reactions, C-H activation, zinc acetylides, tetrasubstituted carbon centers
Number of references:
126
