Cross-coupling reaction: stereoselective synthesis of (E)-aryl or heteroarylvinylgermanes

David-Quillot, Franck; Thibonnet, J.; Marsacq, Didier; Abarbri, Mohamed; Duchêne, Alain

doi:10.1016/s0040-4039(00)01618-x

Cited by 20 publications

(13 citation statements)

References 14 publications

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“…The final building block BB 3 was prepared via initial bromination of commercially-available 9 followed by regio- and stereoselective elimination to generate the novel tri-substituted bromoalkenyl MIDA boronate 10 as a single stereoisomer20 (Scheme 4). Two cycles of our recently developed methodology8e for stereospecific metal-selective cross-coupling with bis-metalated olefin 11 21 followed by stereoretentive iododegermylation22 provided BB 3 .…”

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Stereoretentive Suzuki−Miyaura Coupling of Haloallenes Enables Fully Stereocontrolled Access to (−)-Peridinin

et al. 2010

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Stimulated by the substantial challenge of synthesizing the complex and sensitive stereogenic allene-containing core of (−)-peridinin, the first stereocontrolled coupling of haloallenes with boronic acids has been achieved. This new method and the principles that emerged during its development stand to enable the more efficient and flexible preparation of a wide range of natural products, pharmaceuticals, and intermediates that possess a stereogenic allene motif. This new reaction was harnessed to achieve the first completely stereocontrolled total synthesis of (−)-peridinin. This synthesis was accomplished using only one reaction iteratively to assemble four fully functionalized building blocks with complete stereoretention at each initially halide or boronbearing carbon. This synthesis elevates the capacity of the iterative cross-coupling strategy to an unprecedented benchmark. Moreover, the efficient and highly modular nature of this synthesis promises to enable systematic dissection of the heretofore enigmatic structure/function relationships that underlie the protein-like antilipoperoxidant activities of this remarkable small molecule natural product.Deficiencies of antilipoperoxidant proteins have been associated with atherosclerosis, rheumatoid arthritis, and cancer, and may contribute to an accelerated aging process.1 Small molecules with the capacity to replicate the functions of these proteins could therefore have a major positive impact on human health. In contrast to most carotenoids,2 the C37-norcarotenoid peridinin (1)3 may exert antilipoperoxidant activities primarily through selfpreserving mechanisms, including catalytic quenching of 1 O 2 and decreasing membrane permeability to other reactive oxygen species.4 Isolation from natural sources is very inefficient,3b however, and the sensitive and stereogenic allene moiety central to the structure of 1 has made its stereoselective synthesis very challenging.5 , 6 As a result, the burke@scs.uiuc.edu. Supporting Information Available: Procedures and spectral and crystallographic data (.cif). This material is available free of charge via the Internet at http://pubs.acs.org. Guided by the ICC strategy,8 we applied only SM transforms to retrosynthesize 1 into four building blocks, BB 1 -BB 4 , having all of the required functionality pre-installed in the correct oxidation states and with the desired stereochemical relationships (Scheme 1). We recognized, however, that the disconnection between C8'/C9' corresponded to a stereoretentive SM coupling with a haloallene. Albeit potentially very useful in the preparation of many natural products,9 this was an unprecedented transformation10 that first required development. NIH Public AccessIn related Negishi couplings,11 chloro-and bromoallenes yield products representing net stereochemical inversion, whereas the corresponding iodoallenes tend to favor stereoretention. These results were attributed to two competing mechanisms involving direct oxidative addition (OA) at C-X or indirect S N 2'-like OA12 fol...

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Stereoretentive Suzuki−Miyaura Coupling of Haloallenes Enables Fully Stereocontrolled Access to (−)-Peridinin

et al. 2010

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“…As shown in Scheme 2 A, the approach involves metal-selective cross-coupling of Sn/Ge bis-metalated olefins6 to generate polyenylgermanium intermediates followed by stereospecific iododegermylations 7. To the best of our knowledge, iododegermylations of polyenylgermanium species were unreported.…”

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A Simple and General Platform for Generating Stereochemically Complex Polyene Frameworks by Iterative Cross‐Coupling

2010

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“…5,10,11 In this vein, we recently reported the synthesis of all possible stereoisomeric forms of iododienyl MIDA boronates via the metal-selective cross-coupling of Sn/Ge bis-metalated olefins followed by the stereospecific iododegermylation of the resulting dienylgermanium intermediates. 11,xxiii,xxiv However, the overall efficiency of this process was limited by the low yielding preparation of key building block ( Z )-I- 1 . With the development of the efficient preparation of ( Z )-Br- 1 , we have been able to prepare the dienylgermanium intermediates 21 with substantially improved overall efficiency (Scheme 5).…”

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confidence: 99%

(Z)-(2-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

et al. 2011

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Cross-coupling reaction: stereoselective synthesis of (E)-aryl or heteroarylvinylgermanes

Cited by 20 publications

References 14 publications

Stereoretentive Suzuki−Miyaura Coupling of Haloallenes Enables Fully Stereocontrolled Access to (−)-Peridinin

Stereoretentive Suzuki−Miyaura Coupling of Haloallenes Enables Fully Stereocontrolled Access to (−)-Peridinin

A Simple and General Platform for Generating Stereochemically Complex Polyene Frameworks by Iterative Cross‐Coupling

(Z)-(2-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

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