Palladium-Catalyzed Hydrolysis of Dimethylhydrazone to Carbonyl Compounds

Mino, Takashi; Hirota, T.; Yamashita, Masakazu

doi:10.1055/s-1996-5649

Cited by 15 publications

(3 citation statements)

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“…Ketone DMHs undergo cleavage to the parent ketones by a catalytic amount of Pd(OAc) 2 / SnCl 2 in moderate to good yields. 56 The reaction proceeds without using acidic or oxidative reagents. Even R,βunsaturated ketone DMHs can be hydrolyzed without rearrangement using this catalyst system.…”

Section: Hydrolytic Cleavage Proceduresmentioning

confidence: 99%

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Recovery of Carbonyl Compounds from N,N-Dialkylhydrazones

2000

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Deprotonation of enantiomerically pure hydrazones and subsequent trapping with suitable electrophiles generates new stereogenic centers with excellent stereoselectivity. To liberate the original carbonyl functionality in the final products, it is necessary to cleave the hydrazone moiety. In recent years, many reagents have been developed to regenerate carbonyl compounds from the corresponding dialkylhydrazones which are compatible with a wide range of functionalities. This has allowed the use of hydrazones in the total synthesis of complex natural products. This Account is meant to be an overview of methods which are classified as oxidative, hydrolytic, and reductive cleavage procedures.

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Section: Hydrolytic Cleavage Proceduresmentioning

confidence: 99%

“…Pd(OAc) 2 and SnCl 2 . Ketone DMHs undergo cleavage to the parent ketones by a catalytic amount of Pd(OAc) 2 /SnCl 2 in moderate to good yields . The reaction proceeds without using acidic or oxidative reagents.…”

Section: Hydrolytic Cleavage Proceduresmentioning

confidence: 99%

Recovery of Carbonyl Compounds from N,N-Dialkylhydrazones

2000

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“…Representative results of the cleavage of aromatic, unsaturated, alicyclic and aliphatic ketone dimethylhydrazones are listed in Table 1. 8 When acetophenone dimethylhydrazone 1a was treated with a catalytic amount of Pd(OAc) 2 and SnCl 2 as a co-catalyst in DMF/H 2 O at 70 °C under an air atmosphere, the hydrolyzed compound acetophenone was obtained in good yield (Entry 1). However, when this reaction was carried out under an Ar atmosphere, acetophenone was obtained only in 48% yield after 96 h. When water was absent in this reaction, 1a was not cleaved after 48 h under an air atmosphere, but when the reaction was carried out at 130°C under the same conditions, the corresponding ketone was obtained in 27% yield after 24 h. Therefore, we believe that this reaction proceeded competitively by acidic and oxidative mechanisms.…”

Section: Methodsmentioning

confidence: 99%