title: Total Synthesis of Lycopodium Alkaloids Palhinine A and Palhinine D.
abstract: The first total syntheses of Lycopodium alkaloids palhinine A, palhinine D, and their C3-epimers have been divergently achieved through the use of a connective transform to access a pivotal hexacyclic isoxazolidine precursor. A microwave-assisted regio- and stereoselective intramolecular nitrone-alkene cycloaddition was tactically orchestrated as a key step to install the crucial 10-oxa-1-azabicyclo[5.2.1]decane moiety embedded in the conformationally rigid isotwistane framework, demonstrating the feasibility of constructing the highly strained medium-sized ring by introduction of an oxygen bridging linker to relieve the transannular strain in the polycyclic scaffold. Subsequent N-O bond cleavage provided the synthetically challenging nine-membered azonane ring system bearing the requisite C3 hydroxyl group. Late-stage transformations featuring a chemo- and stereoselective reduction of the pentacyclic β-diketone secured the availability of our target molecules.
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Fang-Xin
authors.initials: FX
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Ji-Yuan
authors.initials: JY
authors.lastname: Du
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Hui-Bin
authors.initials: HB
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Peng-Lin
authors.initials: PL
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Guo-Biao
authors.initials: GB
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Ke-Yin
authors.initials: KY
authors.lastname: Yu
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Xiang-Zhi
authors.initials: XZ
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Xian-Tao
authors.initials: XT
authors.lastname: An
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.
authors.forename: Ye-Xing
authors.initials: YX
authors.lastname: Cao
authors.affiliation: State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University , 222 Tianshui Nanlu, Lanzhou 730000, China.|Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Chun-An
authors.identifier: 0000-0003-4837-3394
authors.initials: CA
authors.lastname: Fan
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
chemical_list: D000470:Alkaloids; C553649:palhinine A