Angewandte
Chemie
[3] H. Shiraki, K. Nishide, M. Node, Tetrahedron Lett. 2000, 41,
Thus, the Wagner–Meerwein rearrangement of the boron
trifluoride etherate of the isoborneol derivative obtained by
reduction of 3l-A, followed by a thiol-exchange reaction in
the presence of odorless 1-dodecanethiol (Dod-SH),[11] gave
4l with 98% ee (Scheme 3).
3437 – 3441.
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Scheme 3. Synthesis of an optically active 1,3-hydroxythiol.
Although the exact role of PFBA is unclear at this stage,
the discovery of PFBA as an additive with an optimum pKa
value will be helpful for the fine tuning of reactions that
involve an aluminum ate complex. In conclusion, we have
reported the asymmetric transformation of the acyclic a,b-
unsaturated ketones 2 into the 1,3-hydroxythiols 4 through
the stereocontrol of three contiguous stereogenic centers.
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Experimental Section
Typical procedure: Dimethylaluminum chloride (solution in hexane,
1.05m, 0.51 mL, 0.54 mmol) was added dropwise to a solution of (ꢀ)-
10-sulfanylisoborneol ((ꢀ)-1; 100 mg, 0.54 mmol) in dichloromethane
(20mL) at 0 8C. The reaction mixture was stirred for 0.5 h, then a
solution of 2 (0.36 mmol) in dichloromethane (5 mL) was added
dropwise (followed by a solution of an additive (0.54 mmol) in
dichloromethane (7 mL), if used), and the mixture was stirred at room
temperature under a nitrogen atmosphere for the time indicated. The
reaction was then quenched with a saturated solution of ammonium
chloride, and the aqueous layer was extracted with ethyl acetate. The
combined organic layers were washed (if an additive was used: with a
saturated solution of sodium hydrogen carbonate, then with brine; in
the absence of an additive: with brine), and were dried over
magnesium sulfate, filtered, and concentrated in vacuo. Purification
of the residue by silica-gel column chromatography (hexane/ethyl
acetate 10:1–20:1) gave 3 as a diastereomeric mixture in the yield
indicated. The diastereomers of 3 were separated by recycling HPLC.
Received: May 16, 2003 [Z51915]
Keywords: asymmetric synthesis · domino reactions ·
.
Michael addition · reduction · synthetic methods
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ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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