Highly enantio- and s-trans C=C bond selective catalytic hydrogenation of cyclic enones: Alternative synthesis of (-)-menthol

Takashi Ohshima, Hiroshi Tadaoka, Kiyoto Hori, Noboru Sayo, Kazushi Mashima

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

A highly enantioselective catalytic hydrogenation of cyclic enones was achieved by using the combination of a cationic Rh1 complex, (S)-5,5′-bis{di(3,5-di-tert-butyl-4-methoxyphenylphosphino)}-4, 4′-bi-1,3-benzodioxole (DTBM-SEGPHOS), and (CH2CH 2PPh3Br)2. The presence of an s-cis C=C bond isopropylidene moiety on the cyclic enone influenced the enantioselectivity of the hydrogenation. Thus, the hydrogenation of 3-alkyl-6-isopropylidene-2- cyclohexen-1-one, which contains both s-cis and s-trans enones, proceeded in excellent enantioselectivity (up to 98% ee). To obtain high enantio- and s-trans selectivities, the addition of a halogen source to the cationic Rh complex was the essential step. With the key step of the s-trans selective asymmetric hydrogenation of piperitenone, we demonstrated a new synthetic method for optically pure (-)-menthol via three atom-economical hydrogenations. Moreover, we found that the complete s-trans and s-cis C=C bond selective reactions were also realized by the proper choice of both the chiral ligands and halides.

Original languageEnglish
Pages (from-to)2060-2066
Number of pages7
JournalChemistry - A European Journal
Volume14
Issue number7
DOIs
Publication statusPublished - Feb 27 2008

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Menthol
Hydrogenation
Enantioselectivity
Halogens
Ligands
Atoms

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Highly enantio- and s-trans C=C bond selective catalytic hydrogenation of cyclic enones : Alternative synthesis of (-)-menthol. / Ohshima, Takashi; Tadaoka, Hiroshi; Hori, Kiyoto; Sayo, Noboru; Mashima, Kazushi.

In: Chemistry - A European Journal, Vol. 14, No. 7, 27.02.2008, p. 2060-2066.

Research output: Contribution to journalArticle

Ohshima, Takashi ; Tadaoka, Hiroshi ; Hori, Kiyoto ; Sayo, Noboru ; Mashima, Kazushi. / Highly enantio- and s-trans C=C bond selective catalytic hydrogenation of cyclic enones : Alternative synthesis of (-)-menthol. In: Chemistry - A European Journal. 2008 ; Vol. 14, No. 7. pp. 2060-2066.
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