163457-34-9Relevant academic research and scientific papers
Synthesis of six-membered compounds by environmentally friendly cyclization using indirect electrolysis
Ihara, Masataka,Katsumata, Akira,Setsu, Fumihito,Tokunaga, Yuji,Fukumoto, Keiichiro
, p. 677 - 684 (1996)
[Ni(cyclam)](ClO4)2-catalyzed indirect electroreduction of olefinic bromides produced six-membered compounds in low to high yields. The synthetic intermediate 49 of Ipecac and Corynanthe alkaloids was obtained in 88% yield in a highly stereoselective manner. Lactam 66, the synthetic precursor of tacamonine, was prepared in 49% yield as a mixture of two diastereoisomers. The electrolysis of the bromoacetates gave the debrominated compounds in good yields.
Chemoenzymatic Total Synthesis and Structural Diversification of Tylactone-Based Macrolide Antibiotics through Late-Stage Polyketide Assembly, Tailoring, and C-H Functionalization
Lowell, Andrew N.,Demars, Matthew D.,Slocum, Samuel T.,Yu, Fengan,Anand, Krithika,Chemler, Joseph A.,Korakavi, Nisha,Priessnitz, Jennifer K.,Park, Sung Ryeol,Koch, Aaron A.,Schultz, Pamela J.,Sherman, David H.
supporting information, p. 7913 - 7920 (2017/06/20)
Polyketide synthases (PKSs) represent a powerful catalytic platform capable of effecting multiple carbon-carbon bond forming reactions and oxidation state adjustments. We explored the functionality of two terminal PKS modules that produce the 16-membered tylosin macrocycle, using them as biocatalysts in the chemoenzymatic synthesis of tylactone and its subsequent elaboration to complete the first total synthesis of the juvenimicin, M-4365, and rosamicin classes of macrolide antibiotics via late-stage diversification. Synthetic chemistry was employed to generate the tylactone hexaketide chain elongation intermediate that was accepted by the juvenimicin (Juv) ketosynthase of the penultimate JuvEIV PKS module. The hexaketide is processed through two complete modules (JuvEIV and JuvEV) in vitro, which catalyze elongation and functionalization of two ketide units followed by cyclization of the resulting octaketide into tylactone. After macrolactonization, a combination of in vivo glycosylation, selective in vitro cytochrome P450-mediated oxidation, and chemical oxidation was used to complete the scalable construction of a series of macrolide natural products in as few as 15 linear steps (21 total) with an overall yield of 4.6%.
Total synthesis of (+)-spiculoic acid A
Matsumura, Daisuke,Toda, Takumi,Hayamizu, Takashi,Sawamura, Kiyoto,Takao, Ken-ichi,Tadano, Kin-ichi
supporting information; experimental part, p. 3356 - 3358 (2009/09/05)
The total synthesis of natural (+)-spiculoic acid A, a new cytotoxic marine natural product of polyketide origin, has been accomplished for the first time. The key step of the total synthesis was a stereoselective and high-yielding intramolecular Diels-Alder reaction of a highly functionalized (E,E,E)-2,7,9-dodecanal derivative for the construction of the core tetrahydroindan-2-one skeleton.
Synthetic studies of microtubule stabilizing agent peloruside A: An asymmetric synthesis of C10-C24 segment
Ghosh, Arun K.,Kim, Jae-Hun
, p. 7659 - 7661 (2007/10/03)
An asymmetric synthesis of the C10-C24 fragment of the potent antitumor macrolide, peloruside A is described. All three stereogenic centers have been enantioselectively constructed utilizing Evans alkylation, Brown asymmetric allylboration, and a substrate controlled epoxide formation. Other key reactions involved Grubbs's ring-closing olefin metathesis and Ando's Z-selective olefination reaction.
Quasiracemic synthesis: Concepts and implementation with a fluorous tagging strategy to make both enantiomers of pyridovericin and mappicine
Zhang, Qisheng,Rivkin, Alexey,Curran, Dennis P.
, p. 5774 - 5781 (2007/10/03)
The concept of quasiracemic synthesis is introduced and illustrated with syntheses of both enantiomers of pyridovericin (whose absolute configuration is assigned as R) and mappicine. Like racemic synthesis, quasiracemic synthesis provides both enantiomers in a single synthetic sequence; however, separation tagging is used to ensure that quasiracemic mixtures can be analyzed, separated, and identified on demand. Fluorous tags of differing chain lengths are used to tag two enantiomeric starting materials. The resulting quasienantiomers are mixed to make a quasiracemate, which is then treated like a true racemate in successive steps of the synthesis. Fluorous chromatography is used to separate, or demix, the final quasiracemate into its two components, which are then detagged to provide (true) enantiomeric products. Quasiracemic synthesis is portrayed as the first and simplest of a series of mixture synthesis techniques based on separation tagging, and the prospects for using other types of separation tags are briefly evaluated.
