Synthesis and characterization of new PNNP-type chiral ligands

Article abstract of DOI:10.1080/10426507.2018.1539997

Polydentate ligands having both soft and hard centers are very effective ligands for the preparation of transition metal complexes. PNNP-type tetradentate diaminodiphosphine ligands are most preferred ligand types cause of their good efficiency for the asymmetric reactions. In this study, three different iminophosphine derivative PNNP-type chiral ligands were synthesized using (R)-(+)-1,1′-Binaphthyl-2,2′-diamine (R-BINAM) and d?phenylphosph?no benzaldehyde derivatives.

Full text of DOI:10.1080/10426507.2018.1539997

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis and characterization of new PNNP-type
chiral ligands
Burcu Tezcan & Bilgehan Güzel
To cite this article: Burcu Tezcan & Bilgehan Güzel (2018): Synthesis and characterization of
new PNNP-type chiral ligands, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2018.1539997
To link to this article: https://doi.org/10.1080/10426507.2018.1539997
Published online: 18 Nov 2018.
Submit your article to this journal
Article views: 8
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=gpss20

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1539997
SHORT COMMUNICATION
Synthesis and characterization of new PNNP-type chiral ligands
€
and Bilgehan Guzel
Burcu Tezcan
Chemistry Department, C¸ukurova University, Adana, Turkey
ABSTRACT
ARTICLE HISTORY
Received 18 September 2018
Accepted 11 October 2018
Polydentate ligands having both soft and hard centers are very effective ligands for the prepar-
ation of transition metal complexes. PNNP-type tetradentate diaminodiphosphine ligands are most
preferred ligand types cause of their good efficiency for the asymmetric reactions. In this study,
three different iminophosphine derivative PNNP-type chiral ligands were synthesized using (R)-
(þ)-1,10-Binaphthyl-2,20-diamine (R-BINAM) and dıphenylphosphıno benzaldehyde derivatives.
KEYWORDS
PNNP type ligand;
iminophosphine;
R-BINAM; chirality
GRAPHICAL ABSTRACT
1
PNNP-type tetradentate diaminodiphosphine ligands are in H NMR spectra characteristic peaks of the imine protons
generally synthesized by the condensation of phosphino- were shifted from 10.50 ppm to 10.44 ppm range. In addition,
aldehydes and imine groups. In this study, firstly, three dif- in 31P NMR spectra, shifts from ꢀ13 ppm to ꢀ15 ppm confirm
ferent phosphinobenzaldehydes (1a-c) were prepared starting the imine bonds on the molecule structures.[2] The bands
from aryl bromides (Scheme 1).[1] Then all of three air-sta- around 1610 cmꢀ1 in FT-IR spectra represent C ¼ N stretching
ble phosphinobenzaldehydes were reacted with R-BINAM in frequencies which are in agreement with the literature.[3]
toluene at reflux temperature using a Dean-Stark apparatus.
All reactions were carried out under dry pure N2 in standard
The resulted iminophosphines (2a-c) which are PNNP type Schlenk apparatus. All the reagents were obtained from commer-
chiral ligands were characterized by spectroscopic methods.
cial suppliers. All solvents were distilled from sodium/benzophe-
1
From H and 31P NMR spectra of compounds (1a-c), the none and stored under nitrogen. The NMR spectra were recorded
typical aldehyde group protons can be found at around on Bruker 400 MHz spectrometer operating at room temperature.
10.60 ppm and the peaks belong to phosphorous atoms can be Infrared spectra were recorded on Thermo FT-IR spectrometer
found at around ꢀ13 ppm as singlet. After the condensation, and Smart ITR diamond attenuated total reflection (ATR).
CONTACT Burcu Tezcan
burcudarendeli@gmail.com
Chemistry Department, C¸ukurova University, Adana 01330, Turkey.
ß 2018 Taylor & Francis Group, LLC

€
B. TEZCAN AND B. GUZEL
2
Scheme 1 Synthesis route of PNNP type chiral ligands.
Disclosure statement
References
No potential conflict of interest was reported by the authors.
[1] Mu€ller, D.; Guꢀenꢀee, L.; Alexakis, A. Practical Synthesis of
SimplePhos Ligands: Further Development of Alkyl-Substituted
Phosphanamines. Eur. J. Org. Chem. 2013, 2013, 6335–6343.
[2] Ligtenbarg, A. G. J.; van den Beuken, E. K.; Meetsma, A.;
Veldman, N.; Smeets, W. J. J.; Spek, A. L.; Feringa, B. L. New
Mono- and Di-Nuclear Complexes of PdII, PtII and NiII of
PNNP Ligands with a 2,20-Biaryl Bridging Unit. J. Chem. Soc.,
Dalton Trans. 1998, 2, 63–270.
Funding
This work was supported by the Scientific Research Projects Program
(BAP No: FDK-2016-5962 and FBA-2018-10690), C¸ukurova
University, Turkey.
[3] Stoop, R. M.; Bachmann, S.; Valentini, M.; Mezzetti, A.
Ruthenium(II) Complexes with Chiral Tetradentate P2N2
Ligands Catalyze the Asymmetric Epoxidation of Olefins with
H2O2. Organometallics. 2000, 19, 4117–4126.
ORCID
Burcu Tezcan
http://orcid.org/0000-0001-5630-5522