Synthesis of anti-1,3-Amino Alcohol Motifs via Pd(II)/SOX catalysis with the Capacity for Stereodivergence
| Autor: | Rulin Ma, Christopher C. Pattillo, Rossella Promontorio, Jonathon Young, Friederike M. Dannheim, M. Christina White |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Organoplatinum Compounds
Stereochemistry Chemistry Alcohol Stereoisomerism General Chemistry Alkenes 010402 general chemistry 01 natural sciences Biochemistry Amino Alcohols Article Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Sulfoxides Oxazines Benzoquinones |
| Popis: | We report the development of a Pd(II)/(±)-MeO-SOX/2,5-dimethylbenzoquinone system that enables unprecedented access to anti-1,3 amino alcohol motifs in good yields (33 substrates, avg. 66% isolated yield, >20:1 dr) and high selectivities (avg. 10:1 dr). Switching ligands to (±)-CF(3)-SOX using a less bulky quinone oxidant, the kinetic syn-1,3 amino alcohol motif can be accessed in comparable yields and selectivities. Advantages of the stereodivergent nature of this reaction are seen in the synthesis of anti- and syn-1,3-amino alcohol vitamin D3 analogue intermediates in half the steps and higher overall yield to previous routes. Additionally, all eight possible stereoisomers of a chiral diamino alcohol core are generated from two amino acids. Mechanistic studies reveal that the anti-isomer is furnished through concurrent Pd(II)(SOX) catalyzed C—H amination and Pd(0)(SOX)-catalyzed isomerization cycles. |
| Databáze: | OpenAIRE |
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