Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+

Kenji Itoh, Katsuyuki Masuda, Takahiko Fukahori, Katsumasa Nakano, Katsuyuki Aoki, Hideo Nagashima

Research output: Contribution to journalArticle

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Abstract

When Cp*Ru(η4-butadiene)X (Cp* = η5-C5Me5; 1a, X = Cl; 1b, X = Br) was treated with excess butadiene in the presence of silver trifluoromethanesulfonate (AgOTf) followed by carbon monoxide (1 atm), 1,5-cyclooctadiene complex [Cp*Ru(η22-C8H12)(CO)]OTf (2) was isolated in 79% yield. Similar [4 + 4] cycloaddition occurred in the reaction of Cp*Ru(η4-isoprene)Cl (1c) with isoprene, AgOTf, and CO to give [Cp*Ru(η22-cis-3,7-dimethyl-1,5-cyclooctadiene)-(CO)]OTf (4a) at ambient temperature. Similar reaction of Cp*Ru(η4-1,3-pentadiene)Cl (1d) with 1,3-pentadiene, however, furnished [Cp*Ru(4-methyl-(1,3-η3:6–8-η3)-nonadienediyl)]OTf (5) in the presence of AgOTf as result of regiospecific linear dimerization. This stoichiometric regioselective dimerization was extended to catalytic formation of 1,5-cyclooctadiene, dimethylcyclooctadienes, and 6-methyl-2,4,7-nonatriene from butadiene, isoprene, or 1,3-pentadiene, respectively, with a catalytic amount of 1b, 1c, or 1d and AgOTf. Alternatively, treatment of butadiene with CpRu(η4-butadiene)Br (Cp = η5-C5H5) and AgOTf induced linear dimerization of butadiene, and [CpRu(η42-1,3,7-octatriene)]OTf (6) was obtained in 98% yield by way of single-step C–C bond formation.

Original languageEnglish
Pages (from-to)1020-1029
Number of pages10
JournalOrganometallics
Volume13
Issue number3
DOIs
Publication statusPublished - Mar 1 1994

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Dimerization
dienes
butadiene
dimerization
Carbon Monoxide
Cycloaddition
cycloaddition
carbon monoxide
ambient temperature
1,3-butadiene
silver
1,5-cyclooctadiene
isoprene
1,3-pentadiene

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+. / Itoh, Kenji; Masuda, Katsuyuki; Fukahori, Takahiko; Nakano, Katsumasa; Aoki, Katsuyuki; Nagashima, Hideo.

In: Organometallics, Vol. 13, No. 3, 01.03.1994, p. 1020-1029.

Research output: Contribution to journalArticle

Itoh, Kenji ; Masuda, Katsuyuki ; Fukahori, Takahiko ; Nakano, Katsumasa ; Aoki, Katsuyuki ; Nagashima, Hideo. / Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+. In: Organometallics. 1994 ; Vol. 13, No. 3. pp. 1020-1029.
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abstract = "When Cp*Ru(η4-butadiene)X (Cp* = η5-C5Me5; 1a, X = Cl; 1b, X = Br) was treated with excess butadiene in the presence of silver trifluoromethanesulfonate (AgOTf) followed by carbon monoxide (1 atm), 1,5-cyclooctadiene complex [Cp*Ru(η2:η2-C8H12)(CO)]OTf (2) was isolated in 79{\%} yield. Similar [4 + 4] cycloaddition occurred in the reaction of Cp*Ru(η4-isoprene)Cl (1c) with isoprene, AgOTf, and CO to give [Cp*Ru(η2:η2-cis-3,7-dimethyl-1,5-cyclooctadiene)-(CO)]OTf (4a) at ambient temperature. Similar reaction of Cp*Ru(η4-1,3-pentadiene)Cl (1d) with 1,3-pentadiene, however, furnished [Cp*Ru(4-methyl-(1,3-η3:6–8-η3)-nonadienediyl)]OTf (5) in the presence of AgOTf as result of regiospecific linear dimerization. This stoichiometric regioselective dimerization was extended to catalytic formation of 1,5-cyclooctadiene, dimethylcyclooctadienes, and 6-methyl-2,4,7-nonatriene from butadiene, isoprene, or 1,3-pentadiene, respectively, with a catalytic amount of 1b, 1c, or 1d and AgOTf. Alternatively, treatment of butadiene with CpRu(η4-butadiene)Br (Cp = η5-C5H5) and AgOTf induced linear dimerization of butadiene, and [CpRu(η4:η2-1,3,7-octatriene)]OTf (6) was obtained in 98{\%} yield by way of single-step C–C bond formation.",
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T1 - Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+

AU - Itoh, Kenji

AU - Masuda, Katsuyuki

AU - Fukahori, Takahiko

AU - Nakano, Katsumasa

AU - Aoki, Katsuyuki

AU - Nagashima, Hideo

PY - 1994/3/1

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N2 - When Cp*Ru(η4-butadiene)X (Cp* = η5-C5Me5; 1a, X = Cl; 1b, X = Br) was treated with excess butadiene in the presence of silver trifluoromethanesulfonate (AgOTf) followed by carbon monoxide (1 atm), 1,5-cyclooctadiene complex [Cp*Ru(η2:η2-C8H12)(CO)]OTf (2) was isolated in 79% yield. Similar [4 + 4] cycloaddition occurred in the reaction of Cp*Ru(η4-isoprene)Cl (1c) with isoprene, AgOTf, and CO to give [Cp*Ru(η2:η2-cis-3,7-dimethyl-1,5-cyclooctadiene)-(CO)]OTf (4a) at ambient temperature. Similar reaction of Cp*Ru(η4-1,3-pentadiene)Cl (1d) with 1,3-pentadiene, however, furnished [Cp*Ru(4-methyl-(1,3-η3:6–8-η3)-nonadienediyl)]OTf (5) in the presence of AgOTf as result of regiospecific linear dimerization. This stoichiometric regioselective dimerization was extended to catalytic formation of 1,5-cyclooctadiene, dimethylcyclooctadienes, and 6-methyl-2,4,7-nonatriene from butadiene, isoprene, or 1,3-pentadiene, respectively, with a catalytic amount of 1b, 1c, or 1d and AgOTf. Alternatively, treatment of butadiene with CpRu(η4-butadiene)Br (Cp = η5-C5H5) and AgOTf induced linear dimerization of butadiene, and [CpRu(η4:η2-1,3,7-octatriene)]OTf (6) was obtained in 98% yield by way of single-step C–C bond formation.

AB - When Cp*Ru(η4-butadiene)X (Cp* = η5-C5Me5; 1a, X = Cl; 1b, X = Br) was treated with excess butadiene in the presence of silver trifluoromethanesulfonate (AgOTf) followed by carbon monoxide (1 atm), 1,5-cyclooctadiene complex [Cp*Ru(η2:η2-C8H12)(CO)]OTf (2) was isolated in 79% yield. Similar [4 + 4] cycloaddition occurred in the reaction of Cp*Ru(η4-isoprene)Cl (1c) with isoprene, AgOTf, and CO to give [Cp*Ru(η2:η2-cis-3,7-dimethyl-1,5-cyclooctadiene)-(CO)]OTf (4a) at ambient temperature. Similar reaction of Cp*Ru(η4-1,3-pentadiene)Cl (1d) with 1,3-pentadiene, however, furnished [Cp*Ru(4-methyl-(1,3-η3:6–8-η3)-nonadienediyl)]OTf (5) in the presence of AgOTf as result of regiospecific linear dimerization. This stoichiometric regioselective dimerization was extended to catalytic formation of 1,5-cyclooctadiene, dimethylcyclooctadienes, and 6-methyl-2,4,7-nonatriene from butadiene, isoprene, or 1,3-pentadiene, respectively, with a catalytic amount of 1b, 1c, or 1d and AgOTf. Alternatively, treatment of butadiene with CpRu(η4-butadiene)Br (Cp = η5-C5H5) and AgOTf induced linear dimerization of butadiene, and [CpRu(η4:η2-1,3,7-octatriene)]OTf (6) was obtained in 98% yield by way of single-step C–C bond formation.

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