Gold-Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones

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Gold-Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones. / Zimin, Dmitry P.; Dar'in, Dmitry V.; Eliseeva, Anastasiya A.; Novikov, Alexander S.; Rassadin, Valentin A.; Kukushkin, Vadim Yu.

In: European Journal of Organic Chemistry, Vol. 2019, No. 35, 22.09.2019, p. 6094-6100.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{18f3756489364b138657e3b12b7bf9ed,

title = "Gold-Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones",

abstract = "Gold-catalyzed functionalization of semicarbazides (ArNHCONHNH2) with various terminal alkynes R2C≡CH (R2 = Alk or Ar) in the presence of Ph3PAuNTf2 (3 mol-%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal-catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid-state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent 1H NMR and 2D NMR and these experiments proved the presence of H-bonds between two molecules. The nature and energy of H-bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06-2X/6-311++G** level of theory.",

keywords = "Alkynes, DFT calculations, Gold catalysis, Hydrogen bonds, Semicarbazone, X-ray, HYDROGEN-BOND, MOLECULAR-STRUCTURE, CRYSTAL-STRUCTURE, COMPLEXES, HYDROAMINATION, HIGHLY EFFICIENT, HYDRATION, DFT COMPUTATIONS, CYCLOISOMERIZATION, CARBOXYLIC-ACIDS",

author = "Zimin, {Dmitry P.} and Dar'in, {Dmitry V.} and Eliseeva, {Anastasiya A.} and Novikov, {Alexander S.} and Rassadin, {Valentin A.} and Kukushkin, {Vadim Yu}",

year = "2019",

month = sep,

day = "22",

doi = "10.1002/ejoc.201901108",

language = "English",

volume = "2019",

pages = "6094--6100",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley-Blackwell",

number = "35",

}

RIS

TY - JOUR

T1 - Gold-Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones

AU - Zimin, Dmitry P.

AU - Dar'in, Dmitry V.

AU - Eliseeva, Anastasiya A.

AU - Novikov, Alexander S.

AU - Rassadin, Valentin A.

AU - Kukushkin, Vadim Yu

PY - 2019/9/22

Y1 - 2019/9/22

N2 - Gold-catalyzed functionalization of semicarbazides (ArNHCONHNH2) with various terminal alkynes R2C≡CH (R2 = Alk or Ar) in the presence of Ph3PAuNTf2 (3 mol-%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal-catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid-state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent 1H NMR and 2D NMR and these experiments proved the presence of H-bonds between two molecules. The nature and energy of H-bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06-2X/6-311++G** level of theory.

AB - Gold-catalyzed functionalization of semicarbazides (ArNHCONHNH2) with various terminal alkynes R2C≡CH (R2 = Alk or Ar) in the presence of Ph3PAuNTf2 (3 mol-%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal-catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid-state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent 1H NMR and 2D NMR and these experiments proved the presence of H-bonds between two molecules. The nature and energy of H-bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06-2X/6-311++G** level of theory.

KW - Alkynes

KW - DFT calculations

KW - Gold catalysis

KW - Hydrogen bonds

KW - Semicarbazone

KW - X-ray

KW - HYDROGEN-BOND

KW - MOLECULAR-STRUCTURE

KW - CRYSTAL-STRUCTURE

KW - COMPLEXES

KW - HYDROAMINATION

KW - HIGHLY EFFICIENT

KW - HYDRATION

KW - DFT COMPUTATIONS

KW - CYCLOISOMERIZATION

KW - CARBOXYLIC-ACIDS

UR - http://www.scopus.com/inward/record.url?scp=85070804259&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/goldcatalyzed-functionalization-semicarbazides-terminal-alkynes-achieve-substituted-semicarbazones

U2 - 10.1002/ejoc.201901108

DO - 10.1002/ejoc.201901108

M3 - Article

AN - SCOPUS:85070804259

VL - 2019

SP - 6094

EP - 6100

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 35

ER -

ID: 45497070