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Abstract
Increasing effort has been made towards the asymmetric total synthesis of rotenoid natural products owing to their impressive biological and pharmaceutical activities. Here we report the modular asymmetric total synthesis of rotenoid natural products. The concise construction of the cis-fused tetrahydrochromeno[3,4-b]chromene core structure of rotenoids through N-heterocyclic carbene-catalyzed dynamic kinetic resolution is achieved, and a series of annulation products containing rotenoid key structures are rapidly assembled using this method. More importantly, the protocol enables the modular synthesis of a variety of rotenoid natural products in a highly convergent fashion, and the concise asymmetric total synthesis of tephrosin, the first asymmetric total synthesis of 12a-hydroxymunduserone, milletosin, and 12a-hydroxyrotenone, and the formal synthesis of deguelin are accomplished.
Highlights
Increasing effort has been made towards the asymmetric total synthesis of rotenoid natural products owing to their impressive biological and pharmaceutical activities
Two methoxy groups at A ring exist in 1a, 1b, 1d, 1e, and 1f; a 1,3-dioxolane moiety occurs in 1c, 1h, and 1g (Fig. 1). These features lead us to the idea that if these natural products can be divided into two pieces, the combination of different pieces will lead to different natural products, simplifying the total synthesis of rotenoid family natural products
The route features first the dynamic kinetic resolution (DKR)-mediated C-C bond formation via asymmetric benzoin reaction, a powerful transformation pioneered by Enders and Suzuki[33,34,35,36,37,38,39,40,41,42,43], and the forge of C-O bond via an SN2 reaction
Summary
Increasing effort has been made towards the asymmetric total synthesis of rotenoid natural products owing to their impressive biological and pharmaceutical activities. The Suh group reported a 12-step enantioselective total synthesis of deguelin (1e) using an iterative pyran-ring formation approach as the key step, and the overall yield of the target was 10.5% (Fig. 2a)[28]. Under these conditions, using Et3N instead of KOH further increased the enantioselectivity of the reaction, but 3a was isolated in only 30% yield (Table 1, entry 19).
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