Article
Chemistry, Multidisciplinary
Akira Hirose, Ayumu Watanabe, Kohei Ogino, Masanori Nagatomo, Masayuki Inoue
Summary: Rhamnofolane, tigliane, and daphnane diterpenoids are structurally complex natural products with multiple oxygen functionalities, and a new synthetic strategy was developed for the total syntheses of five representative members of these families. This unified synthetic route required only 16-20 total steps, demonstrating exceptional efficiency.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Goh Sennari, Kristen E. Gardner, Stefan Wiesler, Maximilian Haider, Alina Eggert, Richmond Sarpong
Summary: Guided by chemical network analysis, the synthetic studies towards C18- and C19-benzenoid cephalotane-type norditerpenoids were carried out, leading to the construction of core structure in a concise manner and improvement of efficiency through reaction optimization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yong Li, Yuxin Cui, Yang Jing, Jun Liu, Yuguo Du
Summary: The enantioselective total syntheses of naturally occurring salicyl alcohols varioxiranol B and varioxiranol C, isolated from the marine-derived fungus Emericella variecolor, have been successfully accomplished for the first time using convergent strategies.
Article
Chemistry, Organic
Hesi Yang, Yan Zhang, Wei Chen, Hongliang Shi, Liang Huo, Jia Li, Huilin Li, Xingang Xie, Xuegong She
Summary: This article describes the first total syntheses of two novel ansamacrolactams, (+/-)-catellatolactams A and B, in 5 and 8 steps, respectively. The synthesis strategy involves an amidation reaction, a regioselective C-H insertion, and an RCM reaction to form the macrocycles with E-olefin. The concise and scalable synthesis provided over 200 mg of the target molecules.
Article
Chemistry, Organic
Takahiro Suzuki, Soichiro Watanabe, Wataru Ikeda, Susumu Kobayashi, Keiji Tanino
Summary: Chloropupukeananin family of compounds are complex bioactive natural products with unique skeletons. The biosynthesis involves a Diels-Alder reaction triggered by specific compounds, although the enzymes responsible have not been identified. A biomimetic synthesis of chloropupukeananin and chloropupukeanolide D has been successfully achieved, indicating a potential role of Diels-Alderases in the biosynthesis of this compound family.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Haiyong Yu, Junhao Zhang, Dongxu Ma, Xiaotong Li, Tao Xu
Summary: This article reports the first enantioselective total synthesis of (-)-caulamidine D and (-)-isocaulamidine D. Their absolute configurations were determined through X-ray crystallography. It was also found that the isolated natural samples exist as TFA salts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pei Qu, Scott A. Snyder
Summary: The newly added annotinolides in the Lycopodium family have complex structures, and we have successfully achieved the total synthesis of three members using key operations such as gold(I)-catalyzed Conia-ene reaction and other challenging transformations. Furthermore, efforts to adjust the oxidation states and rearrange ring systems of the natural products shed light on their potential biogenesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Zhineng Qing, Peng Mao, Tie Wang, Hongbin Zhai
Summary: The total syntheses of cephanolides A-D, featuring a novel tetracyclic core and lactone, have been achieved through substrate-controlled intermolecular Diels-Alder reaction and palladium-catalyzed bimolecular [2 + 2 + 2] cycloaddition reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shicheng Jin, Xiangbo Zhao, Dawei Ma
Summary: The study presents a new method for the synthesis of napelline-type alkaloids, achieving the construction of the core structure and characteristic chemical groups through a series of reactions, including conjugate addition and cyclization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
K. C. Nicolaou, Saiyong Pan, Yogesh Shelke, Stephan Rigol, Ruiyang Bao, Dipendu Das, Qiuji Ye
Summary: A unified synthetic route for the total syntheses of eribulin and a macrolactam analog of halichondrin B has been successfully developed. The synthetic strategy involves the use of a reverse approach to construct cyclic ether structural motifs and a modified intramolecular cyclization reaction to establish the carbon macrocyclic framework of eribulin. These syntheses validate the effectiveness of the reverse approach in constructing cyclic ether structural motifs and provide inspiration and opportunities in the field of halichondrin and related polycyclic ether compounds.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Hiromitsu Shibayama, Yoshihiro Ueda, Takashi Tanaka, Takeo Kawabata
Summary: The total syntheses of punicafolin and macaranganin were achieved in seven steps each, starting from commercial alpha-D-glucose. The key features include sequential site-selective introduction of galloyl groups and stereodivergent construction of the 3,6-HHDP bridge without using protective groups for glucose, resulting in extremely short-step syntheses of natural glycosides with a molecular weight of 938.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Ganxing Huang, Zhengsong Huang, Xianjian Ma, Zhihu Feng, Fengxia Yuan, Song Qin, Shaomin Fu, Bo Liu
Summary: In this study, the asymmetric syntheses of sarbracholide and shizukaol B, two lindenane sesquiterpenoid [4 + 2] head-to-back dimers, were achieved. The synthesis involved a MTBD-mediated one-pot Z-type elimination/lactonization to form an alpha,beta-unsaturated lactone, followed by a biomimetic [4 + 2] dimerization between a triene and dienophile to construct the dimers.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yi Cui, Jun Ren, Jiayuan Lv, Zhongwen Wang
Summary: An efficient synthesis of the aza-[5.7.6.5] tetracyclic core structure of calyciphylline D-type Daphniphyllum alkaloids has been achieved, featuring diastereoselective cyclopropanation and a [3 + 2] IMCC strategy, as well as gram-scale preparation in each step.
Article
Chemistry, Multidisciplinary
Kosuke Okada, Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: The synthesis of (+)-pleiocarpamine, (+)-voacalgine A and (+)-bipleiophylline was achieved in this study. The 10-step synthesis of (+)-pleiocarpamine features the construction of stereochemistry at the C16 position by radical cyclization and the synthesis of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C-H functionalization. By modifying the biomimetic aerobic oxidative coupling of tryptophane derivatives catalyzed by FePc(CO2H)(8), the oxidative coupling of (+)-pleiocarpamine with pyrocatechuic acid produced (+)-voacalgine A. The total synthesis of (+)-bipleiophylline was completed by the second coupling of (+)-voacalgine A with (+)-pleiocarpamine or the one-pot couplings of 2 equiv of (+)-pleiocarpamine with pyrocatechuic acid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jian Xiao, Jun Zhao, Ya-Wen Wang, Gan Luo, Yu Peng
Summary: The first total synthesis of (+)-adunctin C and (+)-adunctin D, two monoterpene-substitued dihydrochalcones isolated from Piper aduncum, was achieved through a regioselective oxidative [3 + 2] cycloaddition of acylphloroglucinol with (-)-beta-phellandrene to construct their unique spiro-benzofuran skeleton. This allowed for the assignment of the absolute configurations of natural adunctins 1 and 2.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Mona Jalali, Farshad Shiri, Alex C. Bissember, Brian F. Yates, Alireza Ariafard
Summary: Density functional theory (DFT) was used to investigate the mechanism of the efficient hydroalkylation of styrene with acetylacetone in the presence of a bismuth catalyst. The results show that the mechanism is fundamentally different from the analogous gold-catalyzed reaction and is characterized by bismuth coordinating to the oxygens of acetylacetone to form a chelated complex. The activation energy for the reaction with bismuth via the enol isomer of acetylacetone is much lower compared to the ketone isomer.
Article
Chemistry, Organic
Nina Gunawan, Michael J. Nutt, Alex C. Bissember, Jason A. Smith, Scott G. Stewart
Summary: Substituted morpholine derivatives are often found in biologically active compounds, making the development of novel synthetic routes towards such structures highly interesting. This study presents the total syntheses of chelonin A, a morpholine-derived marine natural product known for its antibacterial and anti-inflammatory activity. A key step in the synthesis involved the rhodium carbenoid 1,3-insertion into a bromohydrin O-H bond, followed by annulation to form a 2,6-disubstituted-3,4-dihydro-2H-1,4-oxazine core. Furthermore, the study achieved the first asymmetric total synthesis of (-)-chelonin A using an enantioenriched bromohydrin, prepared through asymmetric transfer hydrogenation of an α-bromoketone.
Article
Chemistry, Multidisciplinary
Jackson S. Henneveld, Farshad Shiri, Alireza Ariafard, Nigel T. Lucas, Alex C. Bissember, Bill C. Hawkins
Summary: The investigation and formalization of the distinctive dipole-transmissive dipolar cycloaddition (DTDC) methodology is reported. A DTDC procedure was developed by taking advantage of the structural complementarity of azide and diazoalkane 1,3-dipoles. This method allows for the rapid construction of functionalized polycyclic N-heterocycles through intramolecular azide-alkene 1,3-dipolar cycloadditions followed by N-derivatization and subsequent 1,3-dipolar cycloadditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Angus Olding, Curtis C. Ho, Nigel T. Lucas, Alex C. Bissember
Summary: In this study, a range of unprecedented, kinetically stable alkyl-, alkenyl-, allenyl-, and alkynylpalladium(II) boronates were prepared from various Csp3, Csp2, and Csp electrophiles via a simple, general method. The structures of these complexes were secured by X-ray crystallography, and the chemical competence of a number of these intermediates in transmetalation was demonstrated.
INORGANIC CHEMISTRY
(2023)
Article
Plant Sciences
Thinley Gyeltshen, Bianca J. Deans, Curtis C. Ho, Nathan L. Kilah, Jason A. Smith, Alex C. Bissember
Summary: This study isolated two previously unreported furanosesquiterpenes and three unprecedented gamma-lactone-containing analogues from three Myoporum species. Additionally, nine previously reported furanosesquiterpenes and five other natural products were also isolated. Three distinct types of furanosesquiterpene structures were observed in each of these Myoporum species. Four sesquiterpene natural products, including the lactam-containing sesquiterpene myoporumine A, were synthesized from (-)-ngaione in two steps for each case.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Chemistry, Physical
Alex C. Bissember, Angus Olding, Curtis C. Ho, Nigel T. Lucas, Allan J. Canty
Summary: By covalently tethering a supporting ligand to a boron nucleophile, typically elusive and kinetically unstable Suzuki-Miyaura (SM) pretransmetalation species were able to be controlled. This strategy allowed for the synthesis of an organonickel(II) boronate pretransmetalation intermediate and its characterization through X-ray crystallography. Performing reactions in the presence of carbon monoxide led to pretransmetalation intermediates in carbon-ylative SM reactions-aroylmetal boronates, enabling the determination of the X-ray crystal structures of an aroylnickel(II) boronate (and an aroylpalladium(II) boronate).
Article
Chemistry, Organic
Adriana R. Dutra-Nobre, Wesley J. Olivier, Bianca J. Deans, Nathan L. Kilah, Fernando Maya Alejandro, Jason A. Smith, Alex C. Bissember
Summary: Natural product isolation studies on Dodonaea viscosa revealed significant intraspecific variation in terpene profiles across this species. A total of 14 ent-labdane diterpenoids (including seven previously unreported compounds), four ent-kauranes (including one previously unreported compound), one rare norhopene, and two previously unreported monoterpenoid wax esters were isolated. The proposed structures were elucidated using various spectroscopic techniques and supported by additional analyses such as mass spectrometry and X-ray crystallography.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Thinley Gyeltshen, Wesley J. Olivier, Adriana R. Dutra-Nobre, Nathan L. Kilah, Jason A. Smith, Alex C. Bissember
Summary: Natural products isolation studies on two Dodonaea species led to the discovery of a previously unreported prenylated flavonoid with a malonic acid moiety and several other compounds from the aerial parts of Dodonaea filiformis. In addition, three previously unreported natural products, including another malonic-acid-containing prenylated flavonoid, were found from the flowers of D. viscosa. Furthermore, a revised structure is proposed for a prenylated flavonoid previously isolated from D. viscosa.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Samuel D. Zarfos, Bianca J. Deans, Curtis C. Ho, Gregory J. Jordan, Jason A. Smith, Alex C. Bissember
Summary: This study focused on the isolation of natural products from eight Tasmanian Proteaceae species and three Australian Proteaceae species. Two previously unreported natural products and four rare arbutin esters were identified, supporting the idea that these unique arbutin esters can serve as markers for the chemical evolution of plant species within the Proteaceae family.
CHEMISTRY & BIODIVERSITY
(2023)
Article
Polymer Science
Yeasmin Nahar, Melissa K. Stanfield, Alex C. Bissember, Stuart C. Thickett
Summary: We successfully prepared poly(N-isopropylacrylamide)-block-poly(epsilon-caprolactone) (pNIPAM-b-pCL) block copolymers through simultaneous RAFT polymerization and anionic ring-opening polymerization (ROP) of NIPAM and CL respectively without traditional solvents. The use of a polymerizable eutectic led to higher reaction rates compared to reactions in typical organic solvents, demonstrating the advantage of this synthetic approach.
Article
Chemistry, Multidisciplinary
Angus Olding, Curtis C. Ho, Debabrata Maiti, Alex C. Bissember
Summary: This article explores a series of case studies that examine key strategies enabling the structural authentication of important species in palladium- and nickel-catalysed C-C, C-N, and C-O cross-coupling reactions. It focuses on studies confirming the structures of challenging intermediates using X-ray crystallography, while providing mechanistic insights from these reports.
CHEMICAL COMMUNICATIONS
(2023)
Review
Polymer Science
Melissa K. Stanfield, Rhiannon S. Terry, Jason A. Smith, Stuart C. Thickett
Summary: This review focuses on the use of levoglucosan (LGA) and levoglucosenone (LGO) obtained from cellulose pyrolysis in materials synthesis. It presents various types of polymers, including polyesters, polysaccharides, metathesis-based polymers, and photopolymerized thermosets. The sustainability and environmental impact of these syntheses are also discussed.
