The reaction of allenes with phosphorus(III) compounds bearing a P-NH-(t-Bu) group: isolation of both enantiomers in crystalline form from an achiral system

doi:10.1016/j.tetlet.2008.09.153

Tetrahedron Letters

Volume 49, Issue 50, 8 December 2008, Pages 7135-7138

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Abstract

Structural characterization of the tautomeric forms of the zwitterions proposed in the phosphine catalyzed transformations of electron-deficient allenes by utilizing a cyclodiphosphazane with a P-NH-t-Bu group and Ph₂P(NH-t-Bu) is described. Spontaneous resolution of the products (R and S enantiomers of the crystals) via crystallization is highlighted.

Graphical abstract

The synthesis and spontaneous resolution by crystallization of tautomeric forms of the zwitterions from the reaction of electron-deficient allenes with P^III compounds bearing a P-NH-t-Bu group are described.

Section snippets

Acknowledgments

We thank DST (New Delhi) for financial support and for the Single Crystal X-ray diffractometer facility at the University of Hyderabad, and UGC (New Delhi) for equipment under UPE and CAS programs. NNBK thanks CSIR for a fellowship.

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Phosphine-activated reactions of alkynes/alkenes/allenes as well as the Mitsunobu reaction involve a rich phosphorus chemistry. With the aid of simple cyclodiphosphazanes, characterization of many compounds analogous to the proposed intermediates in such reactions has been accomplished. Use of a cyclodiphosphazane in Pd-catalyzed N-arylation reactions is highlighted. Results on molecular non-stoichiometry in phosphorus compounds and on the use of chiral phosphorus systems are discussed. Synthesis of allenylphosphoramides involving a cyclodiphosphazane is also described. X-ray structures of the new compounds [(t-BuNH)(PhCH₂CH(CN)CH₂–)P(μ-N-t-Bu)₂P(NH-t-Bu)]⁺[HCO₃]⁻ (13), [(t-BuNH)P(μ-N-t-Bu)₂P(N-t-Bu)-C(CH₂)CH(C₆H₄-4-Me)-P(O)(OCH₂CMe₂CH₂O)] (18), [(i-PrNH)P(μ-N-t-Bu)₂P(N-i-Pr)-N(CO₂-i-Pr)-NH(CO₂-i-Pr)] (24), [(S)-(2-OH-1-C₁₀H₆-1′-C₁₀H₆-2′-O-P(O)(NH-t-Bu)₂] (36) and [(t-BuNH)(O)P(μ-N-t-Bu)₂P(O)(CHCCMe₂)] (40) are also reported.

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The reaction of allenes with phosphorus(III) compounds bearing a P-NH-(t-Bu) group: isolation of both enantiomers in crystalline form from an achiral system

Abstract

Graphical abstract

Section snippets

Acknowledgments

Org. Lett.

Org. Lett.

Org. Lett.

ARKIVOC

New J. Chem.

Inorg. Chem.

Acc. Chem. Res.

Synthesis

Acc. Chem. Res.