- Entry to 1,2,3,4-Tetrasubstituted Arenes through Addressing the " Meta Constraint" in the Palladium/Norbornene Catalysis
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Arenes with four different contiguous substituents, i.e. 1,2,3,4-tetrasubstituted arenes, are commonly found in bioactive compounds, but they are nontrivial to access via conventional methods. Through addressing the "meta constraint" in the palladium/norbornene (Pd/NBE) cooperative catalysis, which is the difficulty of tolerating a sizable meta substituent in aryl halide substrates, here a modular and regioselective approach is realized for preparing 1,2,3,4-tetrasubstituted arenes. One key is the use of a C2-amide-substituted NBE, and a combined experimental and computational study reveals its role in promoting the NBE insertion and the ortho C-H metalation steps. The scope is broad: A variety of electrophiles and nucleophiles could be introduced to the ortho and ipso positions, respectively, with 1,4-disubstituted aryl halides, leading to diverse unsymmetrical contiguous tetrasubstituted arenes. Application of this approach has been demonstrated in streamlined syntheses of several bioactive compounds.
- Dong, Guangbin,Liu, Peng,Wang, Jianchun,Xu, Xiaolong,Zhou, Yun
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supporting information
p. 3050 - 3059
(2020/03/10)
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- Studies toward the unique pederin family member psymberin: Full structure elucidation, two alternative total syntheses, and analogs
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Two synthetic approaches to psymberin have been accomplished. A highly convergent first generation synthesis led to the complete stereochemical assignment and demonstrated that psymberin and irciniastatin A are identical compounds. This synthesis featured
- Feng, Yu,Jiang, Xin,De Brabander, Jef K.
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p. 17083 - 17093
(2013/01/15)
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- Synthesis and complete stereochemical assignment of psymberin/irciniastatin for use as antitumor compounds
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The invention relates to the synthesis and complete stereochemical assignments of cytotoxic compounds such as compound 28-a and its stereoisomers: The invention further provides processes for making the compounds, their synthetic intermediates, and for me
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Page/Page column 14
(2010/11/25)
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- Synthesis and complete stereochemical assignment of psymberin/irciniastatin A
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We describe a concise and flexible synthetic avenue for the preparation of compounds with structures relevant to those proposed for the novel marine-derived differential cytotoxins psymberin and irciniastatin A. Our efforts led to their complete stereoche
- Jiang, Xin,Garcia-Fortanet, Jorge,De Brabander, Jef K.
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p. 11254 - 11255
(2007/10/03)
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