Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand

Hu, Bowen; Chen, Dafa; Hu, Xile

doi:10.1002/chem.201304290

Cited by 52 publications

(58 citation statements)

References 89 publications

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“…These NMR data are also very close to those of both terminal CO-and acylmethylpyridine-containing model complexes. 21,24,27 Particularly worth noting is that the 1 H NMR spectra of 9a,b, similar to those of 2-acylmethyl-6-hydroxypyridine ligand-containing complexes, 25,27 exhibited a singlet at 10.08 and 11.62 ppm for their hydroxy groups directly attached to their pyridine rings. However, the two singlets for 9a,b immediately disappeared when D 2 O was added, apparently due to the rapid D/H exchange between 9a,b and D 2 O.…”

Section: ■ Results and Discussionmentioning

confidence: 87%

“…5,6,13−28 Among the previously reported model complexes, those with a 2-acylmethyl-6-hydroxymethylpyridine ligand prepared by us 24 and particularly those with a 2-acymethyl-6-hydroxypyridine ligand prepared by Chen and Hu 25 are of great interest. This is because the natural Hmd enzyme contains a 2-acylmethyl-6-hydroxypyridine moiety, and the hydroxy group in this moiety was reported to play an important role in the activation of dihydrogen.…”

Section: ■ Introductionmentioning

confidence: 99%

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Several New [Fe]Hydrogenase Model Complexes with a Single Fe Center Ligated to an Acylmethyl(hydroxymethyl)pyridine or Acylmethyl(hydroxy)pyridine Ligand

Song

Zhao

et al. 2014

Organometallics

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We have developed two novel synthetic methods, by which two types of mononuclear Fe model complexes for the active site of [Fe]hydrogenase are successfully synthesized. The first type of 2-acylmethyl-6-hydroxymethylpyridine-containing complexes, [2-COCH 2 -6-HOCH 2 C 5 H 3 N]Fe(CO) 2 G (1, G = PhCO 2 ; 2, PhCOS; 3, PhCS 2 ; 4, 2-S-6-MeC 5 H 3 N), were prepared by a "one-pot" method involving reaction of 2-TsO-6-HOCH 2 C 5 H 3 N (Ts = 4-MeC 6 H 4 SO 2 ) with Na 2 Fe(CO) 4 followed by treatment of the resulting Fe(0) intermediate [Na(2-CH 2 -6-HOCH 2 C 5 H 3 N)Fe(CO) 4 ] (M1) with (PhCO 2 ) 2 , (PhCOS) 2 , (PhCS 2 ) 2 , and (2-S-6-MeC 5 H 3 N) 2 in 49−72% yields, respectively. The second type of 2-acylmethyl-6-hydroxypyridine-containing complexes, (2-COCH 2 -6-HOC 5 H 3 N)Fe(CO) 2 (2-SCO-6-RC 5 H 3 N) (9a, R = MeO; 9b, R = PhS), could be prepared via a multiple-step synthetic method. This method involves (i) treatment of 2-ClCO-6-RC 5 H 3 N (R = MeO, PhS) with NaSH followed by acidification with diluted HCl to give 2-HSCO-6-RC 5 H 3 N (5a, R = MeO; 5b, R = PhS); (ii) further treatment of 5a,b with KOH to afford 2-KSCO-6-RC 5 H 3 N (6a, R = MeO; 6b, R = PhS); (iii) treatment of 2-TsOCH 2 -6-PMBOC 5 H 3 N (PMB = 4-MeOC 6 H 4 CH 2 ) with Na 2 Fe(CO) 4 followed by treatment of the resulting Fe(0) intermediate [Na(2-CH 2 -6-PMBOC 5 H 3 N)Fe(CO) 4 ] (M2) with Br 2 or I 2 to produce (2-COCH 2 -6-PMBOC 5 H 3 N)Fe(CO) 3 X (7a, X = Br; 7b, X = I); (iv) further treatment of 7a,b with 6a,b to yield (2-COCH 2 -6-PMBOC 5 H 3 N)Fe(CO) 2 (2-S-6-RC 5 H 3 N) (8a, R = MeO; 8b, R = PhS); and (v) finally, removal of the PMB groups from 8a,b under the action of deprotecting reagent CF 3 CO 2 H/EtSH to give complexes 9a,b. All compounds 1−4 and 5a,b−9a,b with the exception of 7b are new and have been characterized by elemental analysis, spectroscopy, and, particularly for 1, 4, and 7a−9a, X-ray crystallography.

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Section: ■ Results and Discussionmentioning

confidence: 87%

Section: ■ Introductionmentioning

confidence: 99%

Several New [Fe]Hydrogenase Model Complexes with a Single Fe Center Ligated to an Acylmethyl(hydroxymethyl)pyridine or Acylmethyl(hydroxy)pyridine Ligand

Song

Zhao

et al. 2014

Organometallics

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“…Complex 1 (Figure c), the best structural model, is inactive towards H 2 presumably because the 2‐OH group first needs to be deprotonated. However, 1 was unstable when treated with a base . This complex became active only when incorporated into the apo‐enzyme of [Fe]‐hydrogenase .…”

Section: Figurementioning

confidence: 99%

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]‐Hydrogenase

Pan

2020

Angew Chem Int Ed

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[Fe]‐hydrogenase is an efficient biological hydrogenation catalyst. Despite intense research, Fe complexes mimicking the active site of [Fe]‐hydrogenase have not achieved turnovers in hydrogenation reactions. Herein, we describe the design and development of a manganese(I) mimic of [Fe]‐hydrogenase. This complex exhibits the highest activity and broadest scope in catalytic hydrogenation among known mimics. Thanks to its biomimetic nature, the complex exhibits unique activity in the hydrogenation of compounds analogous to methenyl‐H4MPT+, the natural substrate of [Fe]‐hydrogenase. This activity enables asymmetric relay hydrogenation of benzoxazinones and benzoxazines, involving the hydrogenation of a chiral hydride transfer agent using our catalyst coupled to Lewis acid‐catalyzed hydride transfer from this agent to the substrates.

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“…[4,[27][28]71]. Some selected examples are shown in Figure 2, and several of them have very similar structure with the [Fe]-hydrogenase [72][73][74][75][76][77][78][79]. However, until now, none of the [Fe]-hydrogenase models can activate H 2 , even those structurally very similar to the enzyme.…”

Section: Bio-inspired Complexes With An Internal Amine Moietymentioning

confidence: 99%