PMID- 33163781
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20201112
IS  - 2470-1343 (Electronic)
IS  - 2470-1343 (Linking)
VI  - 5
IP  - 43
DP  - 2020 Nov 3
TI  - Catalytic Enantioselective Alkylation of Indoles with 
      trans-4-Methylthio-beta-Nitrostyrene.
PG  - 27978-27989
LID - 10.1021/acsomega.0c03485 [doi]
AB  - The reaction of the rhodium aqua-complex (S (Rh),R (C))-[Cp*Rh(R)-Prophos 
      (OH(2))][SbF(6)](2) [Cp* = C(5)Me(5), Prophos = 
      propane-1,2-diyl-bis(diphenylphosphane)] (1) with 
      trans-4-methylthio-beta-nitrostyrene (MTNS) gives two linkage isomers (S (Rh),R 
      (C))-[Cp*Rh(R)-Prophos(kappa(1) O-MTNS)](2+) (3-O) and (S (Rh),R 
      (C))-[Cp*Rh(R)-Prophos(kappa(1) S-MTNS)](2+) (3-S) in which the nitrostyrene binds 
      the metal through one of the oxygen atoms of the nitro group or through the 
      sulfur atom, respectively. Both isomers are in equilibrium in dichloromethane 
      solution, the equilibrium constant being affected by the temperature in such a 
      way that when the temperature increases, the relative concentration of the 
      oxygen-bonded isomer 3-O increases. The homologue aqua-complex of iridium, (S 
      (Ir),R (C))-[Cp*Ir(R)-Prophos(OH(2))][SbF(6)](2) (2), also reacts with MTNS; 
      but only the sulfur-coordinated isomer (S (Ir),R (C))-[Cp*Ir(R)-Prophos(kappa(1) 
      S-MTNS)](2+) (4-S) is detected in the solution by NMR spectroscopy. The crystal 
      structures of 3-S and 4-S have been elucidated by X-ray diffractometric methods. 
      Complexes 1 and 2 catalyze the Friedel-Crafts reaction of indole, N-methylindole, 
      2-methylindole, or N-methyl-2-methylindole with MTNS. Up to 93% ee has been 
      achieved for N-methyl-2-methylindole. With this indole, the ee increases as 
      conversion increases, ee at 263 K is lower than that obtained at 298 K, and the 
      sign of the chirality of the major enantiomer changes at temperatures below 263 
      K. Detection and characterization of the catalytic intermediates metal-aci-nitro 
      and the free aci-nitro compound as well as detection of the Friedel-Crafts 
      (FC)-adduct complex involved in the catalysis allowed us to propose a plausible 
      double cycle that accounts for the catalytic observations.
FAU - Mendez, Isabel
AU  - Mendez I
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
FAU - Ferrer, Carlos
AU  - Ferrer C
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
FAU - Rodriguez, Ricardo
AU  - Rodriguez R
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
FAU - Lahoz, Fernando J
AU  - Lahoz FJ
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
FAU - Garcia-Orduna, Pilar
AU  - Garcia-Orduna P
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
FAU - Carmona, Daniel
AU  - Carmona D
AD  - Departamento de Quimica Inorganica, Instituto de Sintesis Quimica y Catalisis 
      Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 
      Zaragoza, Spain.
LA  - eng
PT  - Journal Article
DEP - 20201021
PL  - United States
TA  - ACS Omega
JT  - ACS omega
JID - 101691658
PMC - PMC7643163
COIS- The authors declare no competing financial interest.
EDAT- 2020/11/10 06:00
MHDA- 2020/11/10 06:01
PMCR- 2020/10/21
CRDT- 2020/11/09 05:34
PHST- 2020/07/21 00:00 [received]
PHST- 2020/09/16 00:00 [accepted]
PHST- 2020/11/09 05:34 [entrez]
PHST- 2020/11/10 06:00 [pubmed]
PHST- 2020/11/10 06:01 [medline]
PHST- 2020/10/21 00:00 [pmc-release]
AID - 10.1021/acsomega.0c03485 [doi]
PST - epublish
SO  - ACS Omega. 2020 Oct 21;5(43):27978-27989. doi: 10.1021/acsomega.0c03485. 
      eCollection 2020 Nov 3.