TY - JOUR
T1 - Nitrile modulated-Ni(0) phosphines in trans-selective phenylpropenoids isomerization
T2 - An allylic route by a regular η1-N(end-on) or an alkyl route via a flipped-nitrile?
AU - Saputra, Leo
AU - Arifin,
AU - Gustini, Nunik
AU - Sinambela, Novitasari
AU - Indriyani, Nova Pratiwi
AU - Sakti, Aditya Wibawa
AU - Arrozi, Ubed Sonai Fahruddin
AU - Martoprawiro, Muhamad A.
AU - Patah, Aep
AU - Permana, Yessi
N1 - Funding Information:
This work was supported by the Ministry of Education, Culture, Research & Technology, Republic of Indonesia (002/SP2H/PTNBH/DRPM/2019) & PT Inovasi Hijau Indonesia (2021-2022) for the project on essential oils, BPDPSawit (PRJ-36/DPKS/2015) for the support on 1H-NMR 60 MHz – Nanalysis NMReady-60e & Rigaku Miniflex 600 D/teX Ultra, and LPDP Rispro Invitasi (PRJ-75/LPDP/20019) for the support on 31P-NMR 15 MHz – Nanalysis NMReady-60Pro. We acknowledge Master Program Scholarships from Indonesia Endowment Fund (LPDP, 2014-2016), Beasiswa Unggulan (BU-DIKTI, 2016-2017), and Voucher-ITB (2017-2019) for L.S. N.G. and N.S. respectively. Y.P. acknowledges Professor Yana Maolana Syah & Dr Elvira Hermawati (Chemistry Program, ITB) for 1H (500 MHz), 13C (125 MHz) & 31P (202 MHz) NMR measurements, Professor Stephan Irle (Oak Ridge National Laboratory U.S.A) for fruitful discussion on theoretical approaches, and PT Indesso Aroma for fruitful discussion on isoeugenol productions & kind supplies of eugenol, isoeugenol, and methyl eugenol. YP also acknowledges Global Centre for Science and Engineering, Waseda University for additional computational supports (2021-2022). Arifin is grateful for Dispatching Young Researchers Abroad Program, Graduate School of Science, Nagoya University for a short research visit at Chemistry Program, ITB (December 2016-February 2017).
Funding Information:
This work was supported by the Ministry of Education, Culture, Research & Technology, Republic of Indonesia (002/SP2H/PTNBH/DRPM/2019) & PT Inovasi Hijau Indonesia (2021-2022) for the project on essential oils, BPDPSawit (PRJ-36/DPKS/2015) for the support on 1 H-NMR 60 MHz – Nanalysis NMReady-60e & Rigaku Miniflex 600 D/teX Ultra, and LPDP Rispro Invitasi (PRJ-75/LPDP/20019) for the support on 31 P-NMR 15 MHz – Nanalysis NMReady-60Pro. We acknowledge Master Program Scholarships from Indonesia Endowment Fund (LPDP, 2014-2016), Beasiswa Unggulan (BU-DIKTI, 2016-2017), and Voucher-ITB (2017-2019) for L.S., N.G., and N.S., respectively. Y.P. acknowledges Professor Yana Maolana Syah & Dr Elvira Hermawati (Chemistry Program, ITB) for 1 H (500 MHz), 13 C (125 MHz) & 31 P (202 MHz) NMR measurements, Professor Stephan Irle (Oak Ridge National Laboratory U.S.A) for fruitful discussion on theoretical approaches, and PT Indesso Aroma for fruitful discussion on isoeugenol productions & kind supplies of eugenol, isoeugenol, and methyl eugenol. YP also acknowledges Global Centre for Science and Engineering, Waseda University for additional computational supports (2021-2022). Arifin is grateful for Dispatching Young Researchers Abroad Program, Graduate School of Science, Nagoya University for a short research visit at Chemistry Program, ITB (December 2016-February 2017).
Publisher Copyright:
© 2022 Elsevier B.V.
PY - 2022/12
Y1 - 2022/12
N2 - Acetonitrile has been widely viewed as a weakly coordinating solvent in metal-catalyzed reactions. Evidence is presented herein that it worked as an actor ligand in nickel-catalyzed stereoselective isomerizations of eugenol, methyl eugenol, estragole, and allylphenol, with trans-isomerized products of ≥95%. Nickel(0)(nitrile)phosphines were generated in situ from Ni(II) salt in the presence of phosphines, Zn, and nitrile with Ni/phosphines/Zn/nitrile mole ratio as low as 1:2:1:1. The isomerization of eugenol gave trans-isoeugenol of >97% in 30 min at r.t. with Ni turnover frequency (TOF) up to 1,116 h−1 and the activation energy of 61 kJ·mol−1. High selectivity of trans-isoeugenol was retained in continuous and multi-gram trials. Density functional theory (DFT)/PBE0-D3 calculations rationalized the possible formation of nickel hydride (i.e., Ni(H)(η1-CH2CN)(phosphine) complex) from η1-N(end-on)-Ni complex. This nitrile modulated-Ni(0) complex indicated the complex followed an alkyl-type isomerization, instead of a conventional allylic-type one.
AB - Acetonitrile has been widely viewed as a weakly coordinating solvent in metal-catalyzed reactions. Evidence is presented herein that it worked as an actor ligand in nickel-catalyzed stereoselective isomerizations of eugenol, methyl eugenol, estragole, and allylphenol, with trans-isomerized products of ≥95%. Nickel(0)(nitrile)phosphines were generated in situ from Ni(II) salt in the presence of phosphines, Zn, and nitrile with Ni/phosphines/Zn/nitrile mole ratio as low as 1:2:1:1. The isomerization of eugenol gave trans-isoeugenol of >97% in 30 min at r.t. with Ni turnover frequency (TOF) up to 1,116 h−1 and the activation energy of 61 kJ·mol−1. High selectivity of trans-isoeugenol was retained in continuous and multi-gram trials. Density functional theory (DFT)/PBE0-D3 calculations rationalized the possible formation of nickel hydride (i.e., Ni(H)(η1-CH2CN)(phosphine) complex) from η1-N(end-on)-Ni complex. This nitrile modulated-Ni(0) complex indicated the complex followed an alkyl-type isomerization, instead of a conventional allylic-type one.
KW - Alkyl-type isomerizations
KW - DFT/PBE0-D3
KW - Flipped-nitrile
KW - Nickel(nitrile)(phosphines)
KW - Phenylpropenoids isomerization
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U2 - 10.1016/j.mcat.2022.112768
DO - 10.1016/j.mcat.2022.112768
M3 - Article
AN - SCOPUS:85141452235
VL - 533
JO - Molecular Catalysis
JF - Molecular Catalysis
SN - 2468-8231
M1 - 112768
ER -