Dearomatization strategies have been pivotal in the total synthesis of complex natural products, offering efficient pathways to access architecturally intricate molecular frameworks. This review highlights recent advancements in dearomatization methods, emphasizing their utility in creating diverse natural product targets. Key strategies include enzymatic and microbial approaches, such as the chemoenzymatic dearomatization of benzoic acid by A. eutrophus, and the diastereoselective Birch reduction/alkylative dearomatization pioneered by Schultz. These methods have enabled the synthesis of alkaloids like (+)-cepharamine and bisorbicillinoids, demonstrating the versatility of dearomatization in generating chiral building blocks. Oxidative dearomatization, particularly using hypervalent iodine reagents, has been widely applied to phenols and related substrates, leading to the formation of reactive intermediates that undergo cycloadditions and cascade reactions. For example, the oxidative dearomatization of para-alkyl phenols with Oxone yielded para-peroxyquinols, which were further transformed into complex natural products. The oxidative dearomatization of catechols and resorcinols has also been utilized in the synthesis of compounds like (+)-puupehenone and (+)-rishirilide B, showcasing the importance of regioselectivity and diastereoselectivity in these processes. Alkylative dearomatization strategies, such as the alkyative dearomatization of phenols under basic conditions, have been employed to construct polycyclic frameworks. The use of transition-metal complexes, like [RuCp(cod)Cl], in cyclopropanation reactions has facilitated the dearomatization of arenes, as seen in the synthesis of salvileucalin B. Additionally, the [3+2] photocycloaddition of arenes and olefins has been utilized in the synthesis of sesquiterpenoids like (−)-penifulvin A, highlighting the role of photochemical reactions in dearomatization. The synthesis of complex natural products often involves the integration of multiple dearomatization strategies, such as oxidative and alkyative dearomatization, to form C–C and C–S bonds. For instance, the oxidative dearomatization of chiral chloroindane led to the formation of a masked ortho-benzoquinone, which was further transformed into the natural product acutumine. The use of chiral auxiliaries and transition-metal catalysts has been crucial in achieving high enantioselectivity in these processes. In the context of electron-rich heteroarenes, such as furans, pyrroles, and indoles, dearomatization has been employed to construct complex ring systems. The synthesis of stenine involved the use of a domino amido-Pummerer/Diels–Alder sequence, while the total synthesis of merrilactone A utilizedDearomatization strategies have been pivotal in the total synthesis of complex natural products, offering efficient pathways to access architecturally intricate molecular frameworks. This review highlights recent advancements in dearomatization methods, emphasizing their utility in creating diverse natural product targets. Key strategies include enzymatic and microbial approaches, such as the chemoenzymatic dearomatization of benzoic acid by A. eutrophus, and the diastereoselective Birch reduction/alkylative dearomatization pioneered by Schultz. These methods have enabled the synthesis of alkaloids like (+)-cepharamine and bisorbicillinoids, demonstrating the versatility of dearomatization in generating chiral building blocks. Oxidative dearomatization, particularly using hypervalent iodine reagents, has been widely applied to phenols and related substrates, leading to the formation of reactive intermediates that undergo cycloadditions and cascade reactions. For example, the oxidative dearomatization of para-alkyl phenols with Oxone yielded para-peroxyquinols, which were further transformed into complex natural products. The oxidative dearomatization of catechols and resorcinols has also been utilized in the synthesis of compounds like (+)-puupehenone and (+)-rishirilide B, showcasing the importance of regioselectivity and diastereoselectivity in these processes. Alkylative dearomatization strategies, such as the alkyative dearomatization of phenols under basic conditions, have been employed to construct polycyclic frameworks. The use of transition-metal complexes, like [RuCp(cod)Cl], in cyclopropanation reactions has facilitated the dearomatization of arenes, as seen in the synthesis of salvileucalin B. Additionally, the [3+2] photocycloaddition of arenes and olefins has been utilized in the synthesis of sesquiterpenoids like (−)-penifulvin A, highlighting the role of photochemical reactions in dearomatization. The synthesis of complex natural products often involves the integration of multiple dearomatization strategies, such as oxidative and alkyative dearomatization, to form C–C and C–S bonds. For instance, the oxidative dearomatization of chiral chloroindane led to the formation of a masked ortho-benzoquinone, which was further transformed into the natural product acutumine. The use of chiral auxiliaries and transition-metal catalysts has been crucial in achieving high enantioselectivity in these processes. In the context of electron-rich heteroarenes, such as furans, pyrroles, and indoles, dearomatization has been employed to construct complex ring systems. The synthesis of stenine involved the use of a domino amido-Pummerer/Diels–Alder sequence, while the total synthesis of merrilactone A utilized