Preparation of Enantioenriched Alkylcarbastannatranes via Nucleophilic Inversion of Alkyl Mesylates for Use in Stereospecific Cross-Coupling Reactions

Ralph, Glenn; Biscoe, Mark R.

doi:10.1021/acs.organomet.9b00467

Cited by 6 publications

(5 citation statements)

References 26 publications

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“…On the other hand, representatives of these compounds paved its way for different applications . Rather prominent among these is the use of tricarbametallatranes as reagents in organic syntheses , and of inorganic metallatranes lacking any metal–carbon bond as catalysts for polylactide and polyurethane formation. , Furthermore, metallatranes were also used in materials science . Last but not least, the cage-type metallatrane compounds were used as models for academic studies such as nucleophilic substitution at hypercoordinated group XIV element centers , and nontraditional differential mobility behavior…”

Section: Introductionmentioning

confidence: 99%

Extending Chirality in Group XIV Metallatranes

Glowacki-Pallach,

Lutter,

Schollmeyer

et al. 2023

Inorg. Chem.

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The syntheses of the racemic amino alcohol rac-N(CH 2 CMe 2 OH)(CMe 2 CH 2 OH)(CH 2 CHMeOH) (L 22'1d * H 3 , 2) and its representative N(CH 2 CMe 2 OH)(CMe 2 CH 2 OH)(CH 2 C-(R)HMeOH) (L 22'1R H 3 , 3) with the stereogenic carbon center being R-configured are reported. Also reported are the stannatranes L 22'1d * SnOt-Bu (4) L 22'1R SnOt-Bu (6) and germatranes L 22'1d * GeOEt (5) and L 22'1R GeOEt (7) as well as the trinuclear tin oxocluster [(μ 3 -O)(μ 3 -O-t-Bu){SnL 22'1R } 3 ] (8). NMR and IR spectroscopy, electrospray ionization mass spectrometry (ESI MS), and single crystal X-ray diffraction analysis characterize these compounds. Computational studies accompany the experimental work and help understand the diastereoselectivity observed in the course of the metallatrane syntheses.

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Section: Introductionmentioning

confidence: 99%

Extending Chirality in Group XIV Metallatranes

Glowacki-Pallach,

Lutter,

Schollmeyer

et al. 2023

Inorg. Chem.

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“…One emerging interesting application of atrane-type molecules seems to be their use in cross-coupling reactions as a transfer vehicle [ 8 , 9 , 10 , 11 , 12 , 13 ].…”

Section: Introductionmentioning

confidence: 99%

Oligosilanylated Silocanes

et al. 2021

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A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KOtBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides. However, the reaction of the 1,1-bis[tris(trimethylsilyl)silylated] silocane with two equivalents of KOtBu leads to the replacement of one tris(trimethylsilyl)silyl unit with a tert-butoxy substituent followed by silanide formation via KOtBu attack at one of the SiMe3 units of remaining tris(trimethylsilyl)silyl group. For none of the silylated silocanes, signs of hypercoordinative interaction between the nitrogen and silicon silocane atoms were detected either in the solid state. by single crystal XRD analysis, nor in solution by 29Si-NMR spectroscopy. This was further confirmed by cyclic voltammetry and a DFT study, which demonstrated that the N-Si distance in silocanes is not only dependent on the energy of a potential N-Si interaction, but also on steric factors and through-space interactions of the neighboring groups at Si and N, imposing the orientation of the pz(N) orbital relative to the N-Si-X axis.

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“…While carbatranes exhibit not only superior cross-coupling reactivity but also promising orthogonality with organoboron reagents, methods of the synthesis of alkyl carbatranes are fewer than those of alkylboron. 11 Hence, expanding the library of alkyl carbatranes with a complex structure is attractive to synthetic chemistry.…”

Section: Introductionmentioning

confidence: 99%