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Synlett 2007(10): 1622-1624  
DOI: 10.1055/s-2007-980373
LETTER
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Addition of Arylboronic Acids to 2-Methylene-1,3-­dithiane Monoxide

Suguru Yoshida, Hideki Yorimitsu*, Koichiro Oshima*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
Fax: +81(75)3832438; e-Mail: yori@orgrxn.mbox.media.kyoto-u.ac.jp; e-Mail: oshima@orgrxn.mbox.media.kyoto-u.ac.jp;
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Publication History

Received 23 March 2007
Publication Date:
06 June 2007 (online)

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Abstract

Treatment of 2-methylene-1,3-dithiane 1-oxide with arylboronic acid under rhodium catalysis in aqueous dioxane at 25 °C provided the corresponding adduct, which is a useful 2-aryl­alkanal equivalent.

Key words

rhodium - arylboronic acid - addition - methylene dithiane monoxide

    References and Notes

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6

Experimental Procedure
The [Rh(OH)(cod)]2 (7.3 mg, 0.016 mmol) was placed in a flask under an atmosphere of argon. A dioxane (3.0 mL) solution of 2-methylene-1,3-dithiane 1-oxide (1a, 44.1 mg, 0.30 mmol) and H2O (0.3 mL) were added. Then, phenylboronic acid (2a, 43.8 mg, 0.36 mmol) was added, and the mixture was stirred at 25 °C for 3 h. The reaction mixture was poured into sat. aq NaHCO3 (5 mL) and extracted with EtOAc (3 × 10 mL). The combined organic layer was dried over anhyd Na2SO4 and concentrated in vacuo. Purification by chromatography on a silica gel column provided 2-benzyl-1,3-dithiane 1-oxide (3a, 65.6 mg, 0.29 mmol, 97%).

8

The mechanism for the stereoselective formation of the cis-product 3a is not clear at this stage. Protonation of the intermediate shown in Figure [1] would be the key step.

9

The relative stereochemistry of 5 is not clear.

10

We are tempted to assume the stereochemistry of 6b based on the plausible reaction mechanism shown here (Scheme [6] ). Attempts to prepare X-ray-quality crystals of 6b or related compounds are in progress.

12

The relative stereochemistry of 8 has not been determined.