Olivier Abillard[a] and Bernhard Breit
COMMUNICATIONS
Table 3. Domino hydroformylation/cross-aldol addition with
terminal alkenes.
Acknowledgements
This work was supported by the Fonds der Chemischen In-
dustrie, the Deutsche Forschungsgemeinschaft (International
Research Training School “Catalysts and Catalytic Reactions
for Organic Synthesis” GRK 1038) the Alfried Krupp Award
for young university teachers of the Krupp foundation (to
BB).
Entry Product
1
Yield [%][a] dr[b]
ee [%][c]
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2
10:1 99
[a]
Isolated yields of purified cross aldol products (two
steps).
Determined by GC after conversion to the corresponding
acetonide.
[b]
[c]
Determined by chiral GC (Chiraldex (G-TA)).
ploying regioselective hydroformylation with self-as-
sembling catalyst Rh/6-DPPon (L1).
Experimental Section
General Procedure for the Domino Reaction
[Rh(CO)2acac] (7.8 mg, 0.030 mmol), triphenylphosphine
(158.6 mg, 0.604 mmol), l-proline (69.6 mg, 0.604 mmol) and
cyclohexanecarbaldehyde (1.36 g, 12.4 mmol) were dissolved
in DMF (2.2 mL). The solution was transferred to an auto-
clave, pressurized (30 bar, ethylene:H2:CO 1:1:1), and the
reaction mixture stirred for 48 h at 58C. The reaction mix-
ture was then diluted with methanol (16 mL), cooled down
to 08C, and NaBH4 (0.90 g, 24.0 mmol) was added portions-
wise. After the reduction was complete, the reaction mixture
was further diluted with ethyl acetate (50 mL) and hydro-
lyzed with water (20 mL) and saturated aqueous NH4Cl so-
lution (20 mL). The phases were separated and the aqueous
phase was extracted with ethyl acetate (375 mL). The
combined organic phases were washed with brine, dried
(MgSO4) and concentrated under vacuum. Flash chromatog-
raphy of the residue [alumina (deactivated), cylohexane:eth-
yl acetate (from 4:1 to 1:1)] furnished (2R,3S)-3-cyclohexyl-
2-methyl-1,3-propane diol as a colourless oil; yield: 408 mg
(81% based on conversion), 99% ee determined by chiral
GC (for details see Table 1).
Supporting Information
[10] For reviews on hydroformylation see: B. Breit, in: Sci-
ence of Synthesis, Vol. 25. (Ed.: R. Brückner), Georg
Thieme Verlag, Stuttgart, New York, 2007, pp 277–
318; Rhodium Catalyzed Hydroformylation, (Eds.:
Spectroscopic and analytical data for all new compounds as
well as experimental procedures are available as Supporting
Information.
1894
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 1891 – 1895