Identification of Chiral <i>cis‐</i> and <i>trans‐</i>2‐Stannyloxazolidines by Their NMR Spectra and Solid‐State Structures

Cintrat, Jean‐Christophe; Léat‐Crest, Véronique; Parrain, Jean‐Luc; Grognec, Erwan Le; Beaudet, Isabelle; Toupet, Loı̈c; Quintard, Jean‐Paul

doi:10.1002/ejoc.200400203

Cited by 19 publications

(30 citation statements)

References 39 publications

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“…The unambiguous assignment of the cis or trans configurations was established from the multinuclear NMR spectra and X-ray analyses described in the accompanying paper. [44] In all cases, 3-mesyl-or 3-tosyl-2-tributylstannyl-1,3-oxazolidines were obtained in high yields, with strong preferences for the cis isomers, as shown for (R)-phenylglycinol-derived oxazolidines in Scheme 4.…”

Section: Preparation Of 3-sulfonylated 2-tributylstannyl-13-oxazolidmentioning

confidence: 93%

“…[44] The trans isomers are eluted on silica gel (eluent: hexanes/ethyl acetate, 95:5) before their cis isomer counterparts. The trans/ cis nomenclature refers to the relative positions of the group on C 4 and the tributylstannyl group.…”

Section: Preparation Of 3-alkoxycarbonyl-2-tributylstannyl-13-oxazolmentioning

confidence: 99%

“…[44] The trans isomers were eluted before the cis isomers on silica gel (eluent: hexanes/ethyl acetate, 95:5).…”

Section: Preparation Of 3-sulfonylated 2-tributylstannyl-13-oxazolidmentioning

confidence: 99%

“…Detailed NMR characterisation of compounds, allowing cis and trans configuration assignment, and X-ray analyses of one pair of diastereomers are reported separately in the accompanying contribution. [44] …”

Section: Introductionmentioning

confidence: 97%

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Preparation of Chiral 2‐Stannyloxazolidines and First Considerations on the Transacetalisation Reaction Mechanism

et al. 2004

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N‐Protected 2‐tributylstannyl‐1,3‐oxazolidines derived from N‐monoprotected chiral β‐amino alcohols were obtained through transacetalisation of (diethoxymethyl)tributylstannane under acidic conditions. In the case of 4‐substituted 2‐tributylstannyl‐1,3‐oxazolidines, the kinetic product of the reaction was shown to be the trans isomer whatever the nature of the protective group, while the thermodynamic product was the cis isomer in the N‐Ts series and the trans isomer in N‐CO2R compounds. Aspects of the transacetalisation reaction are discussed along with those concerning the isomerisation of the products, allowing an interpretation of the obtained results. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Preparation Of 3-sulfonylated 2-tributylstannyl-13-oxazolidmentioning

confidence: 93%

Section: Preparation Of 3-alkoxycarbonyl-2-tributylstannyl-13-oxazolmentioning

confidence: 99%

“…[44] The trans isomers were eluted before the cis isomers on silica gel (eluent: hexanes/ethyl acetate, 95:5).…”

Section: Preparation Of 3-sulfonylated 2-tributylstannyl-13-oxazolidmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

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Preparation of Chiral 2‐Stannyloxazolidines and First Considerations on the Transacetalisation Reaction Mechanism

et al. 2004

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“…TBs and XBs are depicted as black dotted lines and green dotted lines, respectively. Color code: gray carbon, red oxygen, purple iodine, brown bromine, dark teal tin [54,55] and several other carbonyl derivatives, e.g., amides [56], aldehydes [57,58], and ketones [59].…”

Section: Oxygen Atoms As Tb Acceptorsmentioning

confidence: 99%

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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Modeling indicates the presence of a region of low electronic density (a Bσ-hole^) on group 14 elements, and this offers an explanation for the ability of these elements to act as electrophilic sites and to form attractive interactions with nucleophiles. While many papers have described theoretical investigations of interactions involving carbon and silicon, such investigations of the heavier group 14 elements are relatively scarce. The purpose of this review is to rectify, to some extent, the current lack of experimental data on interactions formed by germanium and tin with nucleophiles. A survey of crystal structures in the Cambridge Structural Database is reported. This survey reveals that close contacts between Ge or Sn and lone-pair-possessing atoms are quite common, they can be either intra-or intermolecular contacts, and they are usually oriented along the extension of the covalent bond formed by the tetrel with the most electron-withdrawing substituent. Several examples are discussed in which germanium and tin atoms bear four carbon residues or in which halogen, oxygen, sulfur, or nitrogen substituents replace one, two, or three of those carbon residues. These close contacts are assumed to be the result of attractive interactions between the involved atoms and afford experimental evidence of the ability of germanium and tin to act as electrophilic sites, namely tetrel bond (TB) donors. This ability can govern the conformations and the packing of organic derivatives in the solid state. TBs can therefore be considered a promising and robust tool for crystal engineering.

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Sn−Li Transmetalation of α‐Aminoorganostannanes for the Stereoselective Synthesis of Substituted Dehydropiperidines and Dehydroazepanes

et al. 2019

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A highly diastereoselective synthesis of (R,S) or (S,S) 2,6-disubstituted dehydropiperidines and 2,7-disubstituted dehydroazepanes has been developed. The stereochemical preference for the (R,S) or the (S,S) isomer is governed by a tin-lithium exchange/electrophilic trapping sequence combined with a ring-closing metathesis. Their relative order was found to have a dramatic influence on the interaction controlling the epimerization at the anionic center. In each case, the complete stereodivergence of the reactions sequence is explained by considering the stabilization brought by the lithium-carbonyl coordination and rationalized by DFT calculations.

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Identification of Chiral cis‐ and trans‐2‐Stannyloxazolidines by Their NMR Spectra and Solid‐State Structures

Cited by 19 publications

References 39 publications

Preparation of Chiral 2‐Stannyloxazolidines and First Considerations on the Transacetalisation Reaction Mechanism

Preparation of Chiral 2‐Stannyloxazolidines and First Considerations on the Transacetalisation Reaction Mechanism

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Sn−Li Transmetalation of α‐Aminoorganostannanes for the Stereoselective Synthesis of Substituted Dehydropiperidines and Dehydroazepanes

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