铜催化的直接型插烯反应研究进展

doi:10.6023/cjoc202201033

摘要/Abstract

插烯反应可以在母体官能团的γ-位(或更远的位置)引入一个新的官能团, 所生成的含有多个官能团的结构单元(尤其是手性结构单元)广泛存在于天然产物、生物活性分子和药物分子中, 并且可用作有机合成的中间体. 因而, 插烯反应(尤其是不对称插烯反应)近年来引起了化学家的广泛关注. 铜作为一种廉价过渡金属, 被广泛用作多种反应的金属催化剂(包括插烯反应). 我们对自己课题组在铜催化的直接型插烯反应领域的研究工作进行了总结. 根据亲电试剂的不同, 将研究分为三部分内容: 不对称插烯羟醛缩合反应、不对称插烯曼尼希反应和插烯氧化羟基化反应. 线性的α,β-或β,γ-不饱和化合物(包括酯、醛酮、酰胺、磷酸酯、砜和腈等)被用作插烯反应中亲核试剂的前体. 通过选用不同的铜催化剂, 反应过程中的区域选择性、非对映选择性和对映选择性得到了较好的控制.

关键词: 插烯反应, 铜催化, 不对称催化, aldol反应, Mannich反应, 氧化羟基化

Vinylogous reaction serves as an efficient tool to introduce a new functional group at the γ-position (or even more remote position) of the parent functional group. The produced highly functionalized structure motifs (especially chiral ones) are ubiquitous in natural products, biologically active compounds and pharmaceuticals. Moreover, they work as important synthetic intermediates in organic syntheses. Therefore, asymmetric vinylogous reaction has gained extensive attention in recent years. Our group is interested in the development of efficient direct vinylogous reactions by using copper catalysts with a focus on the catalytic asymmetric variants. Herein, the advances in our group in this field are reviewed. Both α,β-unsaturated and β,γ-unsaturated compounds (including esters, aldehydes, ketones, phosphonates, sulfones, and nitriles) are used as the vinylogous pronucleophiles. Aldehydes, ketones, imines, and molecular oxygen are employed as the electrophiles. This account is divided into three sections based on the varied electrophiles: asymmetric vinylogous aldol reaction, asymmetric vinylogous Mannich reaction and vinylogous aerobic oxidative hydroxylation. By using suitable copper catalysts, these reactions generally afforded the vinylogous products in good to excellent yields with good to excellent control of regio-, diastereo-, and enantioselectivities.

Key words: vinylogous reaction, copper catalysis, asymmetric catalysis, aldol reaction, Mannich reaction, oxidative hydroxylation

引用此文

李晖, 殷亮. 铜催化的直接型插烯反应研究进展[J]. 有机化学, 2022, 42(6): 1573-1585.

Hui Li, Liang Yin. Research Progress of Copper-Catalyzed Direct Vinylogous Reactions[J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1573-1585.

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图/表 13

Figure 1. Typical commercially available chiral bisphosphine ligands

Scheme 1. Direct catalytic AVAR of linear β,γ-unsaturated esters

Scheme 2. Proposed mechanism for the catalytic AVAR of linear β,γ-unsaturated esters

Scheme 3. Direct catalytic AVAR of allyl phosphonate and sulfone

Scheme 4. Proposed mechanism for the direct catalytic AVAR of allyl phosphonate and sulfone

Scheme 5. Catalytic asymmetric alkynylogous aldol reaction

Scheme 6. Catalytic asymmetric vinylogous aldol-type reaction of allylazaarenes

Scheme 7. Catalytic regioselective asymmetric addition of 1,4-pentadiene to ketones

Scheme 8. Catalytic vinylogous and bisvinylogous Mannich reactions of β,γ-unsaturated N-acylpyrazoles

Scheme 9. Catalytic AVMR of γ-halo-α,β-unsaturated N-acylpyrazoles

Scheme 10. Catalytic diastereoselective AVMR with β,γ-unsaturated and α,β-unsaturated N-acylpyrazoles

Scheme 11. Catalytic vinylogous aerobic oxidative hydroxylation

Scheme 12. Proposed mechanism for the catalytic vinylogous aerobic oxidation

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