Clarification of a remarkable chelate effect leads to palladium-catalyzed base-free olefin arylation

Moshe Portnoy, Yehoshua Ben-David, David Milstein

Research output: Contribution to journalArticle

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Abstract

Palladium-catalyzed, base-free olefin arylation is possible. Thus, reaction of chlorobenzene with styrene and zinc to yield cis-stilbene is catalyzed by Pd-(dippp)2 (2) (or by Pd(OAc)2 + 2dippp; dippp = 1,3-bis(diisopropylphosphino)propane). Other aryl chlorides are also reactive, whereas aryl bromides undergo substantial reduction and coupling. The reaction was discovered as a result of the observation that cis-(dippp)-Pd(Ph)Cl, formed upon oxidative addition of PhCl to 2, reacts with excess styrene (in the presence or absence of base) to generate H2 and yield (dippp)Pd(styrene) and (dippp)PdCl2(5). The latter complex is formed as a result of the instability of the putative cis-(dippp)Pd(H)Cl. 5 can be reduced to Pd(dippp)2 with zinc in the presence of dippp. Pd(dippb)2 (1) (dippb = 1,4-bis(diisopropylphosphino)butane), which yields a trans-oxidative-addition product with PhCl, is inactive in the base-free catalysis, and monophosphines are not effective. This novel reaction is complementary to the normal vinylation of aryl chlorides catalyzed by Pd(dippb)2 under basic conditions, which leads to trans products.

Original languageEnglish
Pages (from-to)4734-4735
Number of pages2
JournalOrganometallics
Volume12
Issue number12
Publication statusPublished - 1993

Fingerprint

Styrene
Palladium
Alkenes
chelates
styrenes
alkenes
palladium
Zinc
Chlorides
zinc
chlorides
Stilbenes
Propane
chlorobenzenes
stilbene
products
butanes
Bromides
propane
Catalysis

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Clarification of a remarkable chelate effect leads to palladium-catalyzed base-free olefin arylation. / Portnoy, Moshe; Ben-David, Yehoshua; Milstein, David.

In: Organometallics, Vol. 12, No. 12, 1993, p. 4734-4735.

Research output: Contribution to journalArticle

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N2 - Palladium-catalyzed, base-free olefin arylation is possible. Thus, reaction of chlorobenzene with styrene and zinc to yield cis-stilbene is catalyzed by Pd-(dippp)2 (2) (or by Pd(OAc)2 + 2dippp; dippp = 1,3-bis(diisopropylphosphino)propane). Other aryl chlorides are also reactive, whereas aryl bromides undergo substantial reduction and coupling. The reaction was discovered as a result of the observation that cis-(dippp)-Pd(Ph)Cl, formed upon oxidative addition of PhCl to 2, reacts with excess styrene (in the presence or absence of base) to generate H2 and yield (dippp)Pd(styrene) and (dippp)PdCl2(5). The latter complex is formed as a result of the instability of the putative cis-(dippp)Pd(H)Cl. 5 can be reduced to Pd(dippp)2 with zinc in the presence of dippp. Pd(dippb)2 (1) (dippb = 1,4-bis(diisopropylphosphino)butane), which yields a trans-oxidative-addition product with PhCl, is inactive in the base-free catalysis, and monophosphines are not effective. This novel reaction is complementary to the normal vinylation of aryl chlorides catalyzed by Pd(dippb)2 under basic conditions, which leads to trans products.

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