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. 2011 Nov 16;133(45):18066-9.
doi: 10.1021/ja207748r. Epub 2011 Oct 21.

Chiral allene-containing phosphines in asymmetric catalysis

Feng Cai  1 , Xiaotao Pu, Xiangbing Qi, Vincent Lynch, Akella Radha, Joseph M Ready
Affiliations

Chiral allene-containing phosphines in asymmetric catalysis

Feng Cai et al. J Am Chem Soc. .

Abstract

We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands.

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Figures

Figure 1
Figure 1
Central, axial and planar stereochemistry in asymmetric catalysis
Figure 2
Figure 2
Structures of Rh(acac)10. a. X-ray crystal structure. Two molecules of pentane and disorder in one -CF3 group have been removed for clarity. b. X-ray crystal structure highlighting key contacts between ligands and Rh. Colors: P: orange; O: red; F: green; Rh: purple; allene highlighted in blue. Images generated with UCSF Chimera. c. Line drawing.
Figure 3
Figure 3
(AllenePhos)M complexes. X-ray structures of complexes formed between AllenePhos ligands and Ag(I) and Pt(II). Colors as in Fig 2. a. Ag-Callene distances: 325 pm and 339 pm. P-Ag-O angle: 164°. C-C-Callene angle: 179°. b. Pt-Callene distances: 221 pm and 209 pm. C-C-C allene angle: 152°. Images generated with UCSF Chimera.
Scheme 1
Scheme 1
Synthesis and structures of allene-containing ligands.
See this image and copyright information in PMC

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