烯丙基重氮重排（ADR）合成芳香双abolanes的不对称方法：(−)-姜黄烯、(−)-二氢姜黄烯、(−)-nuciferol和(−)- nucifernal的全合成

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters Pub Date : 2025-05-19 DOI:10.1016/j.tetlet.2025.155656

Debabrata Mondal , Spoorti B. Patil , Achal Yeola , Vishnumaya Bisai

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引用次数: 0

摘要

摘要以天然存在的双abolane倍半萜，6-羟基-2-甲基-5-（5 ' -羟基-1 ' (R),5 ' -二甲基-己基-3 ' -烯基）-苯酚(4)为原料，通过关键烯丙基二氮基排列（ADR），实现了天然倍半萜的不对称合成。ADR与邻硝基苯磺酰肼发生Mitsunobu反应，邻硝基苯亚磺酸和氮气挤压发生[3,3]异位重排，使磺酰肼加合物分解。该策略已被用于天然存在的倍半萜类化合物(−)-姜黄烯（1a），(−)-二氢姜黄烯（1b），(−)-nuciferol （1c）和(−)-nuciferal （1d）的有效集体全合成。

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Asymmetric approach to aromatic bisabolanes via allylic diazene rearrangement (ADR): Total syntheses of (−)-curcumene, (−)-dihydrocurcumene, (−)-nuciferol, and (−)-nuciferal

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Asymmetric approach to aromatic bisabolanes via allylic diazene rearrangement (ADR): Total syntheses of (−)-curcumene, (−)-dihydrocurcumene, (−)-nuciferol, and (−)-nuciferal

Concise asymmetric approach to the total synthesis of naturally occurring sesquiterpenes have been achieved via a key allylic diazene arrangement (ADR) from a naturally occurring bisabolane sesquiterpenoid, 6-hydroxy-2-methyl-5-(5’-hydroxy-1’(R),5’-dimethyl-hex-3’-enyl)-phenol (4) isolated from the resins of Commiphora kuaa (Burseraceae). The ADR goes through a Mitsunobu reaction with o-nitro benzene sulfonyl hydrazide followed by the decomposition of sulfonyl hydrazide adduct following a [3,3]-sigmatropic rearrangement via the extrusion of o-nitro benzene sulfinic acid and nitrogen gas. This strategy has been utilized for an efficient colelctive total synthesis of naturally occurring sesquiterpenoids, (−)-curcumene (1a), (−)-dihydrocurcumene (1b), (−)-nuciferol (1c) and (−)-nuciferal (1d).

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来源期刊

Tetrahedron Letters 化学-有机化学

CiteScore

3.50

自引率

5.60%

发文量

521

审稿时长

28 days

期刊介绍： Tetrahedron Letters provides maximum dissemination of outstanding developments in organic chemistry. The journal is published weekly and covers developments in techniques, structures, methods and conclusions in experimental and theoretical organic chemistry. Rapid publication of timely and significant research results enables researchers from all over the world to transmit quickly their new contributions to large, international audiences.