钯催化串联反应在含季碳中心的复杂天然产物全合成中的应用

doi:10.6023/cjoc202502022

摘要/Abstract

季碳中心(包含全碳季碳中心和杂原子取代的季碳中心)广泛存在于天然产物及功能分子的核心骨架中, 并且其对分子结构复杂程度的贡献也是非常重要的, 然而, 由于季碳中心本身所具有的复杂的化学结构及显著的空间位阻效应, 使得这类结构单元的合成充满了挑战. 钯催化串联反应在复杂天然产物的环系构建中发挥着非常重要的作用, 其中, 对于分子中季碳中心的合成, 该串联反应表现出了显著的优势. 对近十年来通过钯催化串联反应构筑复杂天然产物中含关键季碳中心的环系, 进而实现对应天然产物全合成的代表性工作进行了详细的综述.

关键词: 钯催化串联反应, 复杂天然产物, 全合成, 季碳中心的构建

Quaternary carbon centers (including all-carbon quaternary centers and heteroatom-contained quaternary carbon centers) are widely present in the core skeletons of natural products and functional molecules, and their contribution to the complexity of molecular structures is also of great significance. However, due to the complex chemical structures and significant steric hindrance effects of quaternary carbon centers, the synthesis of such structural units is fraught with enormous challenges. Palladium-catalyzed cascade reaction plays an important role in the synthesis of the complex natural products. In particular, it shows significant advantages in construction of quaternary carbon centers. The development of application of palladium-catalyzed cascade reaction in the establishment of complex framework with quaternary carbon centers and further total synthesis of corresponding natural products in the last 10 years is introduced.

Key words: palladium-catalyzed cascade reaction, complex natural product, total synthesis, construction of quaternary carbon center

引用此文

赵倩倩, 魏培垚, 刘孙典, 张博鑫, 梁承远. 钯催化串联反应在含季碳中心的复杂天然产物全合成中的应用[J]. 有机化学, 2025, 45(9): 3289-3300.

Qianqian Zhao, Peiyao Wei, Sundian Liu, Boxin Zhang, Chengyuan Liang. Applications of Palladium-Catalyzed Cascade Reactions in Total Synthesis of Complex Natural Products with Quaternary Carbon Centers[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3289-3300.

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图/表 15

图1. 通过钯催化串联反应所合成含季碳天然产物中的代表性分子

Figure 1. Representative molecules of natural products synthesized through palladium-catalyzed cascade reaction

图式1. (＋)-Esermethole (6a)和(＋)-physostigmine (6b)的全合成

Scheme 1. Total synthesis of hexahydropyrroloindole alkaloids (＋)-esermethole (6a) and (＋)-physostigmine (6b)

图式2. 六氢吡咯吲哚生物碱11~13以及15的全合成

Scheme 2. Total synthesis of hexahydropyrroloindole alkaloids 11~13 and 15

图式3. (-)‑N‑Methylwelwitindolinone C isothiocyanate (24)的全合成

Scheme 3. Total synthesis of (-)‑N‑methylwelwitindolinone C isothiocyanate (24)

图式4. 倍半萜(-)-presilphiperfolan-8-ol (32)的全合成

Scheme 4. Total synthesis of (-)-presilphiperfolan-8-ol (32)

图式5. 氧杂螺内酯结构单元合成方法学的建立及C(12)位氧杂半日花烷型二萜α-levantanolide (34a)和α-levantenolide (39)的全合成

Scheme 5. Establishment of synthetic method towards oxaspirolactone unit and total synthesis of the C(12) oxygenated labdanolic diterpenes α-levantanolide (34a) and α-levantenolide (39)

图式6. 百部生物碱48和50的全合成

Scheme 6. Total synthesis of stemona alkaloids 48 and 50

图式7. Cyclopianes二萜的全合成

Scheme 7. Total synthesis of cyclopianes diterpenes

图式8. 二萜类天然产物(＋)-perseanol (72)的全合成

Scheme 8. Total synthesis of (＋)-perseanol (72)

图式9. 单萜吲哚类生物碱schizozygane的全合成

Scheme 9. Total synthesis of schizozygane alkaloids

图式10. 石蒜科生物碱galanthamine (94)和lycoramine (95)的全合成

Scheme 10. Total synthesis of galanthamine (94) and lycoramine (95)

图式11. 莲花烷生物碱metaphanine (104)和oxoepistephamiersine (105)的全合成

Scheme 11. Total synthesis of metaphanine (104) and oxoepistephamiersine (105)

图式12. 二萜类生物碱(-)-garryine (111)的全合成

Scheme 12. Total synthesis of (-)-garryine (111)

图式13. 天然产物euphorbialoid A (119)的全合成

Scheme 13. Total synthesis of euphorbialoid A (119)

图式14. 尼亚那属二萜garajonone (129)的全合成

Scheme 14. Total synthesis of garajonone (129)

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