A comprehensive review of 1411 new MNPs and their structural diversity analysis and including the cyanobacterial metabolite lezoside. 

Marine natural products.

Two series of novel spiro-compounds containing macrolactam or macrolactone and thiadiazoline rings, 1-thia-2-alkylimino-3,4,9-triaza-10-oxospiro[4.15]eicosyl-3-ene (4F) and 1-thia-2-alkylimino-3,4-diaza-9-oxa-10-oxospiro[4.15]eicosyl-3-ene (4G), were synthesized from 12-oxo-1,15-pentadecanlactam and 12-oxo-1,15-pentadecanlactone, respectively. Their structures were confirmed by elemental analysis, 1H NMR, and 13C NMR. The conformation of compounds 4F was determined via the crystal structure of a representative compound (4F6). The bioassay showed that compounds 4F have much better fungicidal activity against five fungi (Botrytis cinerea Pers., Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn., Phomopsis asparagi Sacc., and Pyricularia oryzae Cav.) than compounds 4G. The fact above showed that the presence of a hydrogen-bonding donor for the fungicidal activity of macrocyclic compounds is very important. 4F6 showed excellent fungicidal activity against P. oryzae, which is much better than the commercial fu...

Synthesis, Fungicidal Activity, and Structure−Activity Relationship of Spiro-Compounds Containing Macrolactam (Macrolactone) and Thiadiazoline Rings†

The first and asymmetric total synthesis of bufogargarizins A and B, two unusual and highly oxygenated twin steroids with rearranged A/B rings, was achieved. The synthetically challenging [7-5-6-5] tetracyclic ring system of bufogargarizin A was efficiently constructed by the first intramolecular Ru-catalyzed [5 + 2] cycloaddition reaction of a vinyl ether cyclopropane-yne. Notably, the interesting [5-7-6-5] tetracyclic skeleton of bufogargarizin B was diastereoselectively reassembled by unique retro-aldol/transannular aldol cascade reactions from the [7-5-6-5] tetracyclic framework.

Asymmetric Total Synthesis of Twin Bufogargarizins A and B.

The total syntheses of nine grayanane diterpenoids, namely, GTX-II (1), GTX-III (2), rhodojaponin III (3), GTX-XV (4), principinol D (5), iso-GTX-II (6), 1,5-seco-GTX-Δ1,10-ene (7), and leucothols B (8) and D (9), that belong to five distinct subtypes, were disclosed in a divergent manner. Among them, six members were accomplished for the first time. The concise synthetic approach features three key transformations: (1) an oxidative dearomatization-induced [5 + 2] cycloaddition/pinacol rearrangement cascade to assemble the bicyclo[3.2.1]octane carbon framework (CD rings); (2) a photosantonin rearrangement to build up the 5/7 bicycle (AB rings) of 1-epi-grayanoids; and (3) a Grob fragmentation/carbonyl-ene process to access four additional subtypes of grayanane skeletons. Density functional theory calculations were performed to elucidate the mechanistic origins of the crucial divergent transformation, which combined with late-stage synthetic findings provided insights into the biosynthetic relationships between these diverse skeletons.

Divergent Synthetic Approach to Grayanane Diterpenoids.

ConspectusSteroids continue to play a significant role in organic chemistry, medicinal chemistry, and drug discovery due to their important biological activities and diverse intriguing structures. Although synthetic organic chemists have successfully constructed and elaborated the classical [6–6–6–5] tetracyclic steroid skeleton for nearly a century, synthesis of the unusual rearranged steroids, particularly abeo-steroids with a medium-sized ring, remains a challenge in the synthetic community. Furthermore, the structures of abeo-steroids are complex and diverse, containing a seven-membered ring embedded in the fused or bridged A/B ring system and possessing numerous stereogenic centers. Besides their structural complexity, various abeo-steroids have shown remarkable biological activities. However, the relative scarcity of abeo-steroids in natural sources has impeded the systematic evaluation of their biological activities. In addition, direct strategies to build the core structures of abeo-steroids are very rare, partially because of the high ring-strain energies of their rearranged A/B ring systems. Therefore, the development of direct and efficient synthetic approaches to these complex molecules is highly desired.Our long-standing interest in the total synthesis of abeo-steroids and the development of new cycloaddition reactions for streamlining complex molecule synthesis have led us to develop a series of unique and powerful intramolecular cycloaddition strategies to access a diverse array of highly strained abeo-steroids. These strategies include Ru-catalyzed [5 + 2] cycloaddition, acid-promoted type I [5 + 2] cycloaddition, Rh-catalyzed [2 + 2 + 1] cycloaddition, and type II [5 + 2] cycloaddition. Since 2018, we have accomplished the first total syntheses of five synthetically challenging abeo-steroids, i.e., bufogargarizins A and B, phomarol, bufospirostenin A, and cyclocitrinol, thus facilitating the evaluation of their pharmacological potentials. In this Account, we summarize our laboratory's systematic efforts in the total synthesis of these abeo-steroids via cycloaddition strategies. We highlight the efficiency and versatility of each cycloaddition strategy for constructing structurally complex abeo-steroid cores by forming the A/B ring system. The evolution of each strategy and key lessons learned from the synthetic journey are also discussed. We believe that our unique perspective in this field will promote advances in the total synthesis of abeo- and related steroids. 

Total Synthesis of abeo-Steroids via Cycloaddition Strategy.

Controlling the conformation of medium-sized rings is challenging because of their flexibility and ring strain effects. Herein, we report non-Curtin-Hammett conditions for the precise control of the conformation of cyclodecenones to effect the first cis-selective transannular Prins cyclization, which enabled concise syntheses of the 5(10→1)abeo-steroids bufospirostenin A and ophiopogonol A in only seven steps from inexpensive starting materials. Computational results indicated that the key cyclization was kinetically controlled and proceeded via either a Prins pathway or a carbonyl-ene pathway, depending on the reaction conditions. Moreover, conformational isomerization played a critical role in determining the stereochemistry of the products.

Syntheses of Bufospirostenin A and Ophiopogonol A by a Conformation-Controlled Transannular Prins Cyclization.

Synthesis of 9,11-Secosteroids Pinnisterol E, Glaciasterol B, and 6-Keto-aplidiasterol B.

Phomarol is a structurally unusual 1(10 → 19)abeo-steroid with a pseudo-symmetrical cycloheptene-1,3-diol motif, an aromatic B ring, and a densely functionalized tetrahydropyran ring. Herein, we report a 13-step synthesis of this natural product from inexpensive sitolactone by means of a convergent fragment-coupling approach. Key transformations include a diastereoselective allylboration, a decarboxylative elimination, a Schönecker-Baran C-H hydroxylation, a biomimetic SN2' cyclization, and a late-stage 6π electrocyclization. Mechanistic studies indicate that the pivotal formation of the tetrahydropyran ring occurs via a silyl migration/intramolecular SN2' cyclization cascade rather than via an epoxide-opening process.

Asymmetric Total Synthesis of the Rearranged Steroid Phomarol Enabled by a Biomimetic SN2' Cyclization.

Covering: 2016 to 2023The synthetic chemistry community is always in pursuit of efficient routes to natural products. Among the many available general strategies, skeletal reorganization, which involves the formation, cleavage, and migration of C-C and C-heteroatom bonds, stands out as a particularly useful approach for the efficient assembly of molecular skeletons. In addition, it allows for late-stage modification of natural products for quick access to other family members or unnatural derivatives. This review summarizes efficient syntheses of steroid, terpenoid, and alkaloid natural products that have been achieved by means of this strategy in the past eight years. Our goal is to illustrate the strategy's potency and reveal the spectacular human ingenuity demonstrated in its use and development. 

Controllable skeletal reorganizations in natural product synthesis.

Application of the Radical Polyene Cyclization Reaction in Natural Product Synthesis

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