2023
DOI: 10.1002/asia.202300561
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An Improved Synthesis of PN‐adamantanoid Cages P4(NR)6 and a Mechanistic Study of their Fourfold Oxidation

Michael A. Land,
Jincheng Ren,
Nicholas J. Roberts
et al.

Abstract: Phosphorus‐nitrogen (PN) adamantanoid cages are valuable precursors for materials chemistry, but their syntheses are based on harsh methods that sometimes require access to restricted reagents. We report a new and scalable synthesis of PN adamantanoid compounds by chlorosilane elimination between bis‐silylated amines and phosphorus trichloride. We further study the mechanism of the recently‐reported four‐fold oxidation of such cages with Me3SiN3 to yield tetravalent tetrahedral connectors for materials chemist… Show more

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Cited by 2 publications
(8 citation statements)
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“…81,82 Recently we have reported chlorosilane elimination as an alternative to dehydrochlorination or salt elimination. 83 Specifically, bis-silylated amines RN(SiMe 3 ) 2 (R = Me, n Bu, CH 2 Ph, and CH 2 CH�CH 2 ) react smoothly with PCl 3 in a 6:4 amine:phosphine stoichiometry to eliminate volatile Me 3 SiCl and form derivatives of 1R in 50−95% yields on gram scales (Figure 5a). However, neither of these protocols is suitable to access bulkier derivatives.…”
Section: Syntheses and Stability Of Tetrahedral And Linear Pn Cagesmentioning
confidence: 99%
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“…81,82 Recently we have reported chlorosilane elimination as an alternative to dehydrochlorination or salt elimination. 83 Specifically, bis-silylated amines RN(SiMe 3 ) 2 (R = Me, n Bu, CH 2 Ph, and CH 2 CH�CH 2 ) react smoothly with PCl 3 in a 6:4 amine:phosphine stoichiometry to eliminate volatile Me 3 SiCl and form derivatives of 1R in 50−95% yields on gram scales (Figure 5a). However, neither of these protocols is suitable to access bulkier derivatives.…”
Section: Syntheses and Stability Of Tetrahedral And Linear Pn Cagesmentioning
confidence: 99%
“…Sommer reported the reaction of lithiated benzylamine, LiHNCH 2 Ph, with PCl 3 , as a viable route to 1Bn (Figure a). , Recently we have reported chlorosilane elimination as an alternative to dehydrochlorination or salt elimination . Specifically, bis-silylated amines RN­(SiMe 3 ) 2 (R = Me, n Bu, CH 2 Ph, and CH 2 CHCH 2 ) react smoothly with PCl 3 in a 6:4 amine:phosphine stoichiometry to eliminate volatile Me 3 SiCl and form derivatives of 1R in 50–95% yields on gram scales (Figure a).…”
Section: Three-dimensional Inorganic Cages As Monomers: Phosphorus–ni...mentioning
confidence: 99%
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