PMID- 31750481
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20200103
LR  - 20200108
IS  - 1477-9234 (Electronic)
IS  - 1477-9226 (Linking)
VI  - 49
IP  - 2
DP  - 2020 Jan 2
TI  - Shedding light on the use of Cu(ii)-salen complexes in the A(3) coupling 
      reaction.
PG  - 289-299
LID - 10.1039/c9dt04146j [doi]
AB  - One Cu(ii) complex, Cu(ii)L (1S), has been synthesised, in two high yielding 
      steps under ambient conditions, and characterised by single-crystal X-Ray 
      diffraction (SXRD), IR, UV-Vis, circular dichroism (CD), elemental analysis, 
      thermogravimetric analysis (TGA) and electron spray ionization mass spectroscopy 
      (ESI-MS). This air-stable compound enables the generation, at room temperature 
      and in open-air, of twenty propargylamines, nine new, from secondary amines, 
      aliphatic aldehydes and alkynes with a broad scope with yields up to 99%. 
      Catalyst loadings can be as low as 1 mol%, while the recovered material retains 
      its structural integrity and can be used up to 5 times without loss of its 
      activity. Control experiments, SXRD, cyclic voltammetry and theoretical studies 
      shed light on the mechanism revealing that the key to success is the use of 
      phenoxido salen based ligands. These ligands orchestrate topological control 
      permitting alkyne binding with concomitant activation of the C-H bond and 
      simultaneously acting as a template temporarily accommodating the abstracted 
      acetylenic proton, and continuously generating, via in situ formed radicals and a 
      Single Electron Transfer (SET) mechanism, a transient Cu(i) active site to 
      facilitate this transformation. The scope and limitations of this protocol are 
      discussed and presented.
FAU - Sampani, Stavroula I
AU  - Sampani SI
AD  - Department of Chemistry, School of Life Sciences, University of Sussex, Brighton 
      BN1 9QJ, UK. G.Kostakis@sussex.ac.uk.
FAU - Zdorichenko, Victor
AU  - Zdorichenko V
FAU - Danopoulou, Marianna
AU  - Danopoulou M
FAU - Leech, Matthew C
AU  - Leech MC
FAU - Lam, Kevin
AU  - Lam K
FAU - Abdul-Sada, Alaa
AU  - Abdul-Sada A
FAU - Cox, Brian
AU  - Cox B
FAU - Tizzard, Graham J
AU  - Tizzard GJ
FAU - Coles, Simon J
AU  - Coles SJ
FAU - Tsipis, Athanassios
AU  - Tsipis A
FAU - Kostakis, George E
AU  - Kostakis GE
LA  - eng
PT  - Journal Article
PL  - England
TA  - Dalton Trans
JT  - Dalton transactions (Cambridge, England : 2003)
JID - 101176026
SB  - IM
EDAT- 2019/11/22 06:00
MHDA- 2019/11/22 06:01
CRDT- 2019/11/22 06:00
PHST- 2019/11/22 06:00 [pubmed]
PHST- 2019/11/22 06:01 [medline]
PHST- 2019/11/22 06:00 [entrez]
AID - 10.1039/c9dt04146j [doi]
PST - ppublish
SO  - Dalton Trans. 2020 Jan 2;49(2):289-299. doi: 10.1039/c9dt04146j.