“…Sterner and Johansson reported the first and efficient synthesis of (−)-galiellalactone and established the absolute configuration of the natural product . However, the stereoselective introduction of a tertiary hydroxyl group remains a formidable task because introduction of an epoxide, as a precursor of the tertiary hydroxyl group, into the hydrindane system of 1 has only been reported with moderate diastereoselectivity . In addition, chemical hydroxylation at the central angular position could not directly elaborate the tertiary hydroxyl group…”
An enantioselective total synthesis of (-)-galiellalactone has been accomplished. The key features of the synthesis involve the highly stereoselective construction of the cis-trisubstituted cyclopentane intermediate by a Pd(0)-catalyzed cyclization, the stereospecific introduction of an angular hydroxyl group by Riley oxidation, and the efficient construction of the tricyclic system of (-)-galiellalactone via a combination of diastereoselective Hosomi-Sakurai crotylation and ring-closing metathesis (RCM).
“…Sterner and Johansson reported the first and efficient synthesis of (−)-galiellalactone and established the absolute configuration of the natural product . However, the stereoselective introduction of a tertiary hydroxyl group remains a formidable task because introduction of an epoxide, as a precursor of the tertiary hydroxyl group, into the hydrindane system of 1 has only been reported with moderate diastereoselectivity . In addition, chemical hydroxylation at the central angular position could not directly elaborate the tertiary hydroxyl group…”
An enantioselective total synthesis of (-)-galiellalactone has been accomplished. The key features of the synthesis involve the highly stereoselective construction of the cis-trisubstituted cyclopentane intermediate by a Pd(0)-catalyzed cyclization, the stereospecific introduction of an angular hydroxyl group by Riley oxidation, and the efficient construction of the tricyclic system of (-)-galiellalactone via a combination of diastereoselective Hosomi-Sakurai crotylation and ring-closing metathesis (RCM).
An Efficient Synthesis of Pregaliellalactone (I) and Desoxygaliellalactone (II). -(FURUSETH, E. R.; LARSSON, R.; BLANCO, N.; JOHANSSON, M.; STERNER*, O.; Tetrahedron Lett. 55 (2014) 27, 3667-3669, http://dx.
A palladium‐catalyzed desulfitative arylation reaction of 5‐alkoxy‐3,4‐dibromo‐2(5H)‐furanones to provide 5‐alkoxy‐4‐aryl‐3‐bromo‐2(5H)‐furanones is reported. This reaction has a high reaction site selectivity, which can realize arylation at the C4‐position. Various sodium arylsulfinates are well tolerated under the mild reaction conditions. The current study makes the arylation of general alkenyl halides possible by the use of cheap and easily available sodium arylsulfinates as aryl sources.
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