2014
DOI: 10.1002/asia.201301727
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Silicon‐Based Bulky Group‐Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties

Abstract: Remote stereocontrol through conformational transmission along a carbon chain is highly important in synthetic systems and molecular architectures. In this work, the interactional reactivity between a remote silicon-based bulky group and an O-/N-containing functional group has been revealed and determined by lateral lithiation-substitution, desilylation, as well as desilylation-olefination with benzaldehyde. The results suggest considerable information transmission and steric hindrance that can be exploited fo… Show more

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Cited by 14 publications
(4 citation statements)
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“…Condensation of aldehyde 3 with ( R S )‐ tert ‐butanesulfinamide11 and subsequent 1,2‐addition of Grignard reagent to N ‐ tert ‐butanesulfinyl imine 4 resulted in the formation of a new carbon stereogenic center adjacent to the aromatic amide. Similar to previous work on the synthesis of isolable atropisomeric amides with secondary alcohol or amine moieties,10a we found that the air‐stable syn ‐( R , R S )‐ 5 b and syn ‐( S , R S )‐ 5 b could be obtained easily by flash column chromatography. The X‐ray crystal structures of syn ‐( R , R S )‐ 5 b and syn ‐( S , R S )‐ 5 b confirmed the stereochemistry of the new carbon stereogenic center and the orientation of the amide group (Figure S11 of the Supporting Information, SI).…”
Section: Methodssupporting
confidence: 87%
“…Condensation of aldehyde 3 with ( R S )‐ tert ‐butanesulfinamide11 and subsequent 1,2‐addition of Grignard reagent to N ‐ tert ‐butanesulfinyl imine 4 resulted in the formation of a new carbon stereogenic center adjacent to the aromatic amide. Similar to previous work on the synthesis of isolable atropisomeric amides with secondary alcohol or amine moieties,10a we found that the air‐stable syn ‐( R , R S )‐ 5 b and syn ‐( S , R S )‐ 5 b could be obtained easily by flash column chromatography. The X‐ray crystal structures of syn ‐( R , R S )‐ 5 b and syn ‐( S , R S )‐ 5 b confirmed the stereochemistry of the new carbon stereogenic center and the orientation of the amide group (Figure S11 of the Supporting Information, SI).…”
Section: Methodssupporting
confidence: 87%
“…Numerous strategies have been elaborated for performing regioselective lithiations,3 and the use of the (Me 3 Si) 2 CH group (BTSM)4 was pioneered by Snieckus and was shown to trigger the directed lithiation of benzamides with great efficiency 5. In addition, this bulky silicon group has been successfully used as a remote control in the synthesis of isolable atropisomeric amides by Xia and Xu 6. Recently, the bis(silyl)methyl moiety has also been used for Wittig rearrangements and Prins cyclization 7.…”
Section: Methodsmentioning
confidence: 99%
“…70−72 Stereocontrol relayed by a tertiary aromatic amide from the hydroxy of the ortho-chiral carbon to the newly formed C�C bond on the other ortho-site was discovered. 72 Based on these interesting findings, we turned to the discovery of enantiopure non-biaryl atropisomers bearing additional point chirality. 2 The modular construction strategy was used to synthesize the orthodiphenylphosphaneyl-and formyl-substituted tertiary aromatic amide 54 (Scheme 12).…”
Section: Merging Non-biaryl Atropisomers With Point Chiralitymentioning
confidence: 99%
“…Therefore, as a parallel line to developing multifunctional atropisomers as chiral ligands that superpose axial and central chirality in addition to biaryl atropisomers, our interest in non-biaryl atropisomeric ligands began with the study of the properties of tertiary amide-derived styrenes, which were prepared through lateral sequential lithiation/silylation/olefination reactions directed by neighboring tertiary amides. Stereocontrol relayed by a tertiary aromatic amide from the hydroxy of the ortho -chiral carbon to the newly formed CC bond on the other ortho- site was discovered . Based on these interesting findings, we turned to the discovery of enantiopure non-biaryl atropisomers bearing additional point chirality .…”
Section: Merging Non-biaryl Atropisomers With Point Chiralitymentioning
confidence: 99%