Reaction of allyl and benzyl Grignard reagents with functionalized nitroalkanes affords nitrones in good yield. This process shows considerable chemoselectivity; carbonyl groups and other highly reactive electrophilic functions are unaffected by the reaction conditions (THF, -70 "C). A mixture of regioisomers 4 and 5 is usually obtained, and the product distribution depends on the nature of the alkyl framework. An intermediate 3 is postulated, and the isomeric pair of nitrones arises, very likely through a selective syn elimination. a-Substituted alkyl chaina give mostly conjugated products 4 while unbranched chains afford predominantly the nonconjugated nitrones 5. The 4 f 5 ratio can be strongly modified by using a proton source of suitable strength; trichloroacetic acid produces 4 exclusively in the reaction of nitroethane with benzyl Grignard, while 2,6-dimethylphenol affords completely the nonconjugated nitrone 5. The stereochemistry of the double bond is affected by the nature of the reagent used. Benzyl Grignard gives only 2 nitrones 4 and 5; 2-butenylmagnesium chloride gives nonconjugated 2 nitrones and a predominance of E isomer in the conjugated nitrone 5.

Nitrones from Addition of Benzylic and Allylic Grignard Reagents to Alkyl Nitro Compounds: Chemo- Regio- and Stereoselectivity of the Reaction.”

BARTOLI, Giuseppe;MARCANTONI, Enrico;PETRINI, Marino
1992

Abstract

Reaction of allyl and benzyl Grignard reagents with functionalized nitroalkanes affords nitrones in good yield. This process shows considerable chemoselectivity; carbonyl groups and other highly reactive electrophilic functions are unaffected by the reaction conditions (THF, -70 "C). A mixture of regioisomers 4 and 5 is usually obtained, and the product distribution depends on the nature of the alkyl framework. An intermediate 3 is postulated, and the isomeric pair of nitrones arises, very likely through a selective syn elimination. a-Substituted alkyl chaina give mostly conjugated products 4 while unbranched chains afford predominantly the nonconjugated nitrones 5. The 4 f 5 ratio can be strongly modified by using a proton source of suitable strength; trichloroacetic acid produces 4 exclusively in the reaction of nitroethane with benzyl Grignard, while 2,6-dimethylphenol affords completely the nonconjugated nitrone 5. The stereochemistry of the double bond is affected by the nature of the reagent used. Benzyl Grignard gives only 2 nitrones 4 and 5; 2-butenylmagnesium chloride gives nonconjugated 2 nitrones and a predominance of E isomer in the conjugated nitrone 5.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11581/241371
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact