Elsevier eBooks, Journal Year: 2023, Volume and Issue: unknown, P. 335 - 356
Published: Dec. 19, 2023
Language: Английский
Science, Journal Year: 2023, Volume and Issue: 381(6653), P. 75 - 81
Published: July 6, 2023
Skeletal ring enlargement is gaining renewed interest in synthetic chemistry and has recently focused on insertion of one or two atoms. Strategies for heterocyclic expansion through small-ring remain elusive, although they would lead to the efficient formation bicyclic products. Here, we report a photoinduced dearomative thiophenes by bicyclo[1.1.0]butanes produce eight-membered rings under mild conditions. The value, broad functional-group compatibility, excellent chemo- regioselectivity were demonstrated scope evaluation product derivatization. Experimental computational studies point toward photoredox-induced radical pathway.
Language: Английский
Citations
115
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1262 - 1268
Published: Jan. 5, 2024
A concise enantioselective total synthesis of (−)-daphenylline, a hexacyclic Daphniphyllum alkaloid with unique benzene ring, was achieved in 14 steps. The commences two chiral stereocenters, C2 and C18, readily installed via Carreira's Ir/amine dual-catalyzed allylation. allylic bridgehead amine 6 rapidly prepared through Wickens' photoredox-catalyzed hydrocarboxylation olefin CuBr2-catalyzed α-amination ketone. tetracycle 4 formed Pd-catalyzed reductive Heck reaction or, more concisely, by Krische's Rh-catalyzed 1,6-enyne cyclization. In this synthesis, newly reported used twice, Friedel–Crafts acylation thrice.
Language: Английский
Citations
11
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26569 - 26579
Published: Nov. 30, 2023
The macrodaphniphyllamine-type, calyciphylline A-type, daphnilongeranin and daphnicyclidin D-type alkaloids are four structurally related classes of Daphniphyllum alkaloids. On the basis a systematic analysis biogenetic network these classes, we developed synthetic strategies centered on C4–N C1–C8 bonds A, which took full advantage suitable substrates, reactions, pathways that altered from their counterparts in postulated network. Through this generalized biomimetic approach, achieved first synthesis 14 subfamilies.
Language: Английский
Citations
19
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2928 - 2932
Published: Jan. 30, 2024
The asymmetric total synthesis of pedrolide (>200 mg) with an unprecedented [5–5–5–6–6–3] hexacyclic core (pedrolane) was achieved. Its unique bicyclo[2.2.1]heptane ring system efficiently constructed via enantioselective ene reaction cyclopentadiene followed by a Wittig reaction, isomerization, and diastereoselective intramolecular Diels–Alder cascade. highly oxygenated carane [6–3] synthesized ring-closing metathesis unusual free carbene cyclopropanation. Furthermore, the 12 contiguous stereocenters were installed diastereoselectively.
Language: Английский
Citations
6
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21170 - 21175
Published: Aug. 22, 2023
The first total syntheses of polycyclic diterpenes phomopsene (1), methyl phomopsenonate (2), and iso-phomopsene (3) have been accomplished through the unusual cascade reorganization C-C single bonds. This approach features: (i) a synergistic Nazarov cyclization/double ring expansions in one-step, developed by authors, to rapid stereospecific construction 5/5/5/5 tetraquinane scaffold bearing contiguous quaternary centers (ii) one-pot strategic expansion Beckmann fragmentation/recombination efficiently assemble requisite 5/5/6/5 tetracyclic skeleton target molecules 1-3. work enables us determine that correct structure is, fact, C7 epimer originally assigned structure. Finally, absolute configurations three were confirmed enantioselective synthesis.
Language: Английский
Citations
11
Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(6), P. 109229 - 109229
Published: Oct. 24, 2023
Language: Английский
Citations
11
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25445 - 25450
Published: Sept. 5, 2024
To date, it remains challenging to precisely and efficiently construct structurally intriguing polycarbocycles with densely packed stereocenters in organic synthesis. Niduterpenoid B, a naturally occurring ERα inhibitor, exemplifies this complexity its intricate polycyclic network comprising 5 cyclopentane 1 cyclopropane rings, featuring 13 contiguous stereocenters, including 4 all-carbon quaternary centers. In work, we describe the first total synthesis of niduterpenoid B using structural reorganization strategy. Key features include following: (1) an efficient methoxy-controlled cascade reaction that forges highly functionalized tetraquinane (A-D rings) bearing sterically hindered stereocenters; (2) rhodium-catalyzed [1 + 2] cycloaddition facilitates construction strained 3/5 bicycle (E-F angularly fused ring D.
Language: Английский
Citations
4
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 20, 2024
In this report, we detail two distinct synthetic approaches to calyciphylline A-type
Language: Английский
Citations
4
Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 104 - 104
Published: Jan. 1, 2025
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 19, 2025
A synthetic route to the highly functionalized tetracyclic core framework of daphlongamine B is described. Key features strategy involve an oxidative dearomatization-induced [4+2] cycloaddition, a di-π-methane rearrangement, and ring-closing metathesis reaction. Our approach enables reliable construction fully elaborated precursor, which, in turn, provides valuable functional handles for further elaboration target molecule.
Language: Английский
Citations
0