Journal of the American Chemical Society
Article
alkene (Table 3, entry 6). Thus, to our delight the yield of C9-
alcohols was improved to 82% and the regioselectivity to 86:14.
Next, the scope and limitations of this ruthenium-catalyzed
isomerization/hydroformylation/reduction sequence were ex-
amined on 13 examples of industrially important aliphatic as
well as various functionalized internal olefins (Table 4). We
were pleased to find that simple internal alkenes (2-pentene, 2-
hexene, 3-hexene) reacted well to give linear alcohols in high
yield and regioselectivity (Table 4, entries 1−4). On the other
hand, 4-octene gave only 14% yield with poor regioselectivity
(Table 4, entry 5). Interesting building blocks for polymers
were obtained in moderate to good yields from internal alkenes
bearing hydroxyl or nitrile groups (Table 4, entries 6 and 7).
Although cyclic olefins often show low reactivity in carbon-
ylation reactions, a good result was obtained with cyclohexene
as a substrate (Table 4, entry 8). Similarly, 2,5-dihydrofuran
gave a good yield but only moderate regioselectivity (Table 4,
entry 9). 2,3-Dihydrofuran, which represents an enol ether
substrate, provided reverse regioselectivity in comparison to
2,5-dihydrofuran (Table 4, entry 10). Furthermore, the Boc-
group-protected cyclic enamine was transformed to the product
in moderate yield but good regioselectivity (Table 4, entry 11).
With (1E)-1-propenylbenzene, a mixture of three different
alcohols was obtained (Table 4, entry 12). When limonene was
used as the substrate, the internal double bond remained intact
and only the double bond in the side chain was selectively
hydroformylated to the corresponding alcohol with good
results (Table 4, entry 13).
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are particularly grateful to the Bundesministerium fur
̈
Bildung und Forschung (the German Federal Ministry of
Education and Research) for financial support under the
PROFORMING project (No. 03X3559) and the Deutsche
Forschungsgemeinschaft (Leibniz-price), Chinese Scholarship
council (grants for L.W.), Swiss National Science Foundation
(SNSF, grants for I.F.) and Evonik Industries AG. We thank
Dr. Christine Fischer, Susann Buchholz, Susanne Schareina,
Andreas Koch, and Dr. Wolfgang Baumann for their technical
and analytical support. We are grateful to Dr. Qiang Liu, MSc.
Xianjie Fang, and MSc. Jola Pospech for helpful discussions.
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ASSOCIATED CONTENT
* Supporting Information
Text, tables, and figures giving synthetic details as well as ligand
and product data. This material is available free of charge via
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dx.doi.org/10.1021/ja4060977 | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX