Stereospecific Cross-Coupling of Secondary Organotrifluoroborates: Potassium 1-(Benzyloxy)alkyltrifluoroborates

Molander, Gary A.; Wisniewski, Steven R.

doi:10.1021/ja307861n

Cited by 186 publications

(119 citation statements)

References 74 publications

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“…43 These materials could be prepared in high enantiomeric purity, and in contrast to 2°alkyl systems (eq 30), the cross-coupling transpired with retention of configuration with extremely high stereochemical fidelity. A rationale for both the stereochemistry of the transmetalation and the lack of β-hydride elimination/ isomerization that often accompanies 2°alkyl cross-coupling was proposed.…”

Section: Scheme 1 Detailed Mechanism Of Aryltrifluoroborate Crosscoumentioning

confidence: 99%

Organotrifluoroborates: Another Branch of the Mighty Oak

2015

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Over the past two decades, organotrifluoroborates have evolved from being chemical curiosities to important reagents for the elaboration of organic molecules. Aside from their often-unique reactivity patterns, favorable features of these reagents include their ease of preparation/isolation, reliable crystallinity, enhanced stability, and monomeric structure. Currently >600 structurally diverse reagents of this class are commercially available, and >850 such compounds have been reported from the author's laboratory. The organotrifluoroborates can be utilized as shelf-stable precursors to a variety of end products through simple functional group transformations and have also been employed as partners in cross-coupling reactions between aromatic, alkenyl, alkynyl, and alkyl substrates in library or individual formats. Within the realm of cross-coupling reactions, organotrifluoroborates provide a practical entry to substructural entities not readily accessed using other organometallic reagents, and most recently, the development of a novel mechanistic paradigm for cross-coupling promises to expand the range of accessible cross-coupling partners even further to include both single- and two-electron processes.

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Section: Scheme 1 Detailed Mechanism Of Aryltrifluoroborate Crosscoumentioning

confidence: 99%

Organotrifluoroborates: Another Branch of the Mighty Oak

2015

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“…When using chiral secondary alkylboron intermediates, these issues are compounded by the challenge of stereocontrol (control of the configuration of a stereogenic carbon). Indeed, although some progress has been realized in recent years [7][8][9][10][11][12][13][14][15][16][17][18][19][20] , control of stereoselectivity is viewed as one of the final frontiers in the Suzuki Miyaura reaction (Fig. 1b) 21 .…”

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confidence: 99%

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

2014

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Non-aromatic nitrogen-and oxygen-containing heterocycles such as piperidines and pyrans are prevalent components of natural products and pharmaceutical drugs. Although it has been a workhorse as a synthetic method for assembling unsaturated sp 2 -hybridized substrates, transition metal-catalysed cross-coupling chemistry is traditionally not a suitable approach to prepare chiral non-aromatic heterocycles. Several mechanistic issues hamper the coupling of stereogenic secondary sp 3 -hybridized carbon-metal centres. Moreover, use of unsymmetrical allylic boronates in the Suzuki Miyaura cross-coupling is further complicated by the possibility of forming two regioisomeric products. Here we address this two-pronged problem and demonstrate that chiral enantiomerically enriched heterocyclic allylic boronates can be coupled with high stereochemical retention with a wide variety of aryl and alkenyl halides to independently afford both regioisomeric 2-and 4-substituted dihydropyrans and dehydropiperidines in high selectivity. A divergent mechanism is proposed where regiochemistry is governed by the nature of the ligands on the palladium catalyst. This scalable method is applied to the efficient preparation of the neuroactive alkaloid anabasine and the antidepressant drug paroxetine.

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“…The benzyloxy group is thought to prevent competing β-hydride elimination by acting as a hemilabile ligand [77]. Prior research has demonstrated that these types of ligands can serve several roles in the prevention of β-hydride elimination.…”

Section: Stereoselective Couplings Of Alkyl Boronates With Aryl or Almentioning

confidence: 99%

At the Forefront of the Suzuki–Miyaura Reaction: Advances in Stereoselective Cross-Couplings

Sun

Hall

2015

Topics in Organometallic Chemistry

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Stereospecific Cross-Coupling of Secondary Organotrifluoroborates: Potassium 1-(Benzyloxy)alkyltrifluoroborates

Cited by 186 publications

References 74 publications

Organotrifluoroborates: Another Branch of the Mighty Oak

Organotrifluoroborates: Another Branch of the Mighty Oak

Synthesis of chiral heterocycles by ligand-controlled regiodivergent and enantiospecific Suzuki Miyaura cross-coupling

At the Forefront of the Suzuki–Miyaura Reaction: Advances in Stereoselective Cross-Couplings

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