Enantioselective installation of adjacent tertiary benzylic stereocentres using lithiation–borylation–protodeboronation methodology. Application to the synthesis of bifluranol and fluorohexestrol

Roesner, Stefan; Blair, Daniel J.; Aggarwal, Varinder K.

doi:10.1039/c4sc03901g

Cited by 50 publications

(22 citation statements)

References 43 publications

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“…86 Amination followed by amide formation furnished the core of (+)-kalkitoxin in an overall 52% yield. This same approach has been used to synthesize baulamycin A, 87 tatanan A, 88 fluorohexestrol, 89 and C30 botryococcene 90 and many other targets. 91 More broadly, the versatility of this homologation method, which tolerates a diversity of structural variation in its building blocks, opens the door for divergent synthesis.…”

Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the customized approach currently used to synthesize this class of chemical matter. In contrast, the “building block approach”, i.e., generalized iterative assembly of interchangeable parts, has now proven to be a highly efficient and flexible way to construct things ranging all the way from skyscrapers to macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that improve access to specific classes of small molecules. There has also been substantial recent progress toward the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes, and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small molecule synthesis may be within reach.

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Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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“…Chemie propanol (1P2P) and 2-phenyl-1-propanol (2P1P) to investigate the chiral discrimination of our CMOM family towards their racemic mixtures.E nantiopure phenylpropanols are important intermediates used in the synthesis of pharmaceutical and parasiticide compounds. [16] Chiral resolution experiments were conducted using our previously reported procedure [5b] on activated CMOM crystals (see the Experimental Section in the Supporting Information for full details). The activated crystals were soaked in racemic mixtures of phenylpropanols for 5days before the crystalline solids were filtered and washed with cyclohexane to remove the excess of molecules adsorbed on the external surface.W et hen extracted the encapsulated phenylpropanols from the crystals using dichloromethane and we evaluated the enantioselective separation performance by analyzing the composition of the eluate through HPLC.…”

Section: Methodsmentioning

confidence: 99%

Structural Elucidation of the Mechanism of Molecular Recognition in Chiral Crystalline Sponges

2020

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To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S‐mandelate)2(4,4′‐bipyridine)3](NO3)2, CMOM‐1S, is a modular MOF; five new variants in which counterions (BF4−, CMOM‐2S) or mandelate ligands are substituted (2‐Cl, CMOM‐11R; 3‐Cl, CMOM‐21R; 4‐Cl, CMOM‐31R; 4‐CH3, CMOM‐41R) and the existing CF3SO3− variant CMOM‐3S are studied herein. Fine‐tuning of pore size, shape, and chemistry afforded a series of distinct host–guest binding sites with variable chiral separation properties with respect to three structural isomers of phenylpropanol. Structural analysis of the resulting crystalline sponge phases revealed that host–guest interactions, guest–guest interactions, and pore adaptability collectively determine chiral discrimination.

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“…B. in Cyclopropanierungen [7] oder Homologisierungsreaktionen. [8] Jedoch führt das gleichzeitige Vorhandensein von einem Metall und einer Abgangsgruppe zu einer inhärenten thermischen Labilität. Im Falle der Lithium-und Magnesiumcarbenoide finden Zersetzungsreaktionen durch Metallsalzeliminierungen häufig bei niedrigen Temperaturen statt, was eine kontrollierte Handhabung und Isolierung erschwert, sodass viele Transformationen immer noch mit in situ hergestellten Reagenzien durchgeführt werden.…”

Section: Introductionunclassified

Lösungsmitteleinflüsse auf die Struktur und Stabilität von Alkalimetallcarbenoiden

et al. 2020

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Enantioselective installation of adjacent tertiary benzylic stereocentres using lithiation–borylation–protodeboronation methodology. Application to the synthesis of bifluranol and fluorohexestrol

Abstract: Highly hindered benzylic carbamates have been reacted with hindered boronic esters to give tertiary boronic esters with very high diastereo- and enantiocontrol and the methodology has been applied to otherwise difficult-to-access molecules.

Cited by 50 publications

References 43 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

Structural Elucidation of the Mechanism of Molecular Recognition in Chiral Crystalline Sponges

Lösungsmitteleinflüsse auf die Struktur und Stabilität von Alkalimetallcarbenoiden

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