高鏡像選擇性銠(I)/掌性雙烯配體催化芳香基硼酸對反丁烯二酸酯進行不對稱1,4加成反應及其合成應用 -α2腎上腺素受體拮抗劑全合成 -氮-苄基-3-苯基吡咯啶的不對稱合成

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2011

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Abstract

  利用天然物左旋醋酸冰片酯49合成高穩定性的掌性雙環[2.2.1]雙烯配體,並結合銠(I)催化芳香基硼酸對反丁烯二酸酯進行不對稱1,4-加成反應。在這個催化系統中,銠(I) (1mol% of Rh)催化量和掌性雙烯配體進行不對稱1,4-加成反應,產物具有高產率和高立體選擇性(高達>99.5% ee值)。並將其應用在合成掌性3-(2-甲氧基)苯基吡咯啶(α2 -腎上腺素受體拮抗劑)和合成掌性氮-苄基-3-苯基吡咯啶。
A new set of stable chiral bicyclo[2.2.1] diene ligands were prepared from (-)-bornyl acetate 49, and were employed in the rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to fumarates. In this catalytic system, rhodium-diene complex (1.0 mol%) generated in situ from chiral diene 53a and [RhCl(C2H4)2]2 successfully yielded the corresponding adducts with good to excellent chemical yields and excellent levels of enantioselectivities (up to >99.5% ee). This methodology was demonstrated by its utilization in the enantioselective total synthesis of 3-(2-methoxyphenyl)pyrrolidine (an α2-adrenoceptor antagonist) and asymmetric synthesis of N-benzyl-3-phenylpyrrolidine.

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, 反丁烯二酸酯, 不對稱1, 4-加成, rhodium, fumarate, asymmetric 1, 4-addition

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