26059-40-5Relevant articles and documents
Sulfonium-Based Homolytic Substitution Observed for the Radical SAM Enzyme HemN
Deng, Zixin,Ding, Wei,Ji, Wenjuan,Ji, Xinjian,Mandalapu, Dhanaraju,Sun, Peng,Zhang, Qi
supporting information, p. 8880 - 8884 (2020/04/01)
Sulfur-based homolytic substitution (SH reaction) plays an important role in synthetic chemistry, yet whether such a reaction could occur on the positively charged sulfonium compounds remains unknown. In the study of the anaerobic coproporphyrinogen III oxidase HemN, a radical S-adenosyl-l-methionine (SAM) enzyme involved in heme biosynthesis, we observed the production of di-(5′-deoxyadenosyl)methylsulfonium, which supports a deoxyadenosyl (dAdo) radical-mediated SH reaction on the sulfonium center of SAM. The sulfonium-based SH reactions were then investigated in detail by density functional theory calculations and model reactions, which showed that this type of reactions is thermodynamically favorable and kinetically competent. These findings represent the first report of sulfonium-based SH reactions, which could be useful in synthetic chemistry. Our study also demonstrates the remarkable catalytic promiscuity of the radical SAM superfamily enzymes.
Stereoselective synthesis of a: Podophyllum lignan core by intramolecular reductive nickel-catalysis
Xiao, Jian,Cong, Xiao-Wei,Yang, Gui-Zhen,Wang, Ya-Wen,Peng, Yu
supporting information, p. 2040 - 2043 (2018/03/01)
A Ni-catalyzed reductive cascade to a diastereocontrolled construction of THN[2,3-c]furan, is developed. The mild reaction conditions led to the tolerance of broad functional groups that can be placed in almost every position of this skeleton with good yields. The conformational control for the observed trans- or cis-fused selectivity during this tandem cyclization-coupling is also proposed.
Macrolactonization of Alkynyl Alcohol through Rh(I)/Yb(III) Catalysis
Zhang, Wen-Wen,Gao, Tao-Tao,Xu, Li-Jin,Li, Bi-Jie
supporting information, p. 6534 - 6538 (2018/10/20)
A catalytic macrolactonization through oxidative cyclization of alkynyl alcohol by synergistic transition-metal and Lewis-acid catalysis was developed. Because the alkynyl alcohol substrates involved in this method are different from the seco acids that are used in conventional macrolactonization methods, the current method provides a strategically distinct entry to macrolactones. In addition to the operational simplicity, this macrolactonization protocol proceeds at relatively high concentration, precluding the need for high dilution or slow addition procedures.
