91028-08-9Relevant academic research and scientific papers
Assembly of Complex Macrocycles by Incrementally Amalgamating Unprotected Peptides with a Designed Four-Armed Insert
Curtin, Brice H.,Manoni, Francesco,Park, Jiyong,Sisto, Luke J.,Lam, Yu-Hong,Gravel, Michel,Roulston, Anne,Harran, Patrick G.
, p. 3090 - 3108 (2018)
We describe the asymmetric synthesis of a highly substituted ω-octynoic acid derivative and demonstrate its utility for generating complex macrocycles from unprotected peptides. The molecule harbors an isolated quaternary center that displays four uniquely functionalized arms, each of which can be reacted orthogonally in sequence as the molecule is integrated into peptide structure. These processing sequences entail (1) scaffold ligation, (2) macrocyclization via internal aromatic alkylations or catalyzed etherifications, (3) acyliminium ion mediated embedding of condensed heterocycles, and (4) terminal alkyne derivatization or dimerization reactions. Numerous polycycles are prepared and fully characterized in this study. Factors that influence reaction efficiencies and selectivity are also probed. We construct a novel mimic of the second mitochondria derived activator of caspase using these techniques, wherein subtle variations in macrocycle connectivity have a marked impact on performance. In general, the chemistry is an important step toward facile, systematic access to complex peptidomimetics synthesized by directly altering the structure and properties of machine-made oligomers.
Photoredox-Catalyzed α-Aminoalkylcarboxylation of Allenes with CO2
Hahm, Hyungwoo,Baek, Doohyun,Kim, Dowon,Park, Seongwook,Ryoo, Jeong Yup,Hong, Sukwon
supporting information, p. 3879 - 3884 (2021/05/29)
The photoredox-catalyzed α-aminoalkylcarboxylation of aryl allenes with CO2 and N,N-dimethylanilines is reported for the first time (26 examples, up to 96% yield). In the case of electron-deficient allenes, good regioselectivity was observed (up to 94:6), exclusively generating kinetic products over thermodynamic products. This protocol is a novel synthetic method for highly functionalized β,γ-unsaturated γ-aminobutyric esters.
Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters
Ye, Fei,Wang, Chengpeng,Ma, Xiaoshen,Hossain, Mohammad Lokman,Xia, Ying,Zhang, Yan,Wang, Jianbo
, p. 647 - 652 (2016/09/12)
Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w
Some reactions of gem-dibromocyclopropanes and metal carbonyls
Lin, Shaw-Tao,Lee, Chuan-Chen,Ding, Mei-Fang,Liang, David W.,Jeng, An-Ting
scheme or table, p. 529 - 534 (2012/08/08)
A series of gem-dibromocyclopropanes were treated with various metal complexes. Among the metal complexes, Ru(CO)2(PPh3) 3, Ru(CO)3(PPh3)2, and Mo(CO) 6 were able to remove a bro
Suzuki-miyaura cross coupling reactions of b-Allenyl-9-BBN
Radkowski, Karin,Seidel, Guenter,Fuerstner, Alois
experimental part, p. 950 - 952 (2011/12/05)
Despite the tremendously wide scope of the palladiumcatalyzed SuzukiMiyaura cross coupling, boron-based allenylation reactions of aryl halides are virtually unknown. It is now demonstrated that the borate complex formed in situ from B-allenyl-9-BBN and NaOMe in DMF allows aryl- and heteroaryl iodides to be allenylated under mild conditions.
One-pot chemoselective functionalization of arylsilanes via cascade metal-metal exchange reactions
Hupe, Eike,Calaza, M. Isabel,Knochel, Paul
, p. 1390 - 1391 (2007/10/03)
A cascade-transmetallation sequence allows a one-pot conversion of arylsilanes into functionalized arylcoppers; they react with various types of electrophiles (allylic halides, acid chlorides, bromoalkynes); bimetallic zinc-copper-reagents can be prepared by this method either directly or in a sequential fashion.
