Rights statement: This is the author’s version of a work that was accepted for publication in Tetrahedron Letters. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Tetrahedron Letters, 57, 32, 2016 DOI: 10.1016/j.tetlet.2016.06.131
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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Palladium-catalyzed construction of quaternary carbon centers with propargylic electrophiles
AU - Franckevicius, Vilius
N1 - This is the author’s version of a work that was accepted for publication in Tetrahedron Letters. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Tetrahedron Letters, 57, 32, 2016 DOI: 10.1016/j.tetlet.2016.06.131
PY - 2016/8/10
Y1 - 2016/8/10
N2 - This short review describes the broad reactivity of propargylic electrophiles with nucleophiles under palladium catalysis for the construction of quaternary carbon centers, leading to allenylation, propargylation, and alkenylation/allylic alkylation. Although the allenylation and propargylation of a nucleophile can readily create congested carbon centers, these processes often compete and require careful tuning of substrate structure and reactivity of the nucleophile. The alkenylation/allylic alkylation sequence is a much more studied reactivity mode, which results in the coupling of two nucleophiles. This approach is very popular for the rapid generation of molecular complexity, but also poses several chemo- and regioselectivity issues. These selectivity problems have been traditionally overcome by tethering strategies and cyclization reactions. However, over the past few years, highly selective intermolecular coupling reactions of nucleophiles have also been developed. It is, therefore, unsurprising that, as our prowess to control selectivity has grown, the first methods for the palladium-catalyzed enantioselective installation of quaternary carbon centers with propargylic electrophiles have also appeared.
AB - This short review describes the broad reactivity of propargylic electrophiles with nucleophiles under palladium catalysis for the construction of quaternary carbon centers, leading to allenylation, propargylation, and alkenylation/allylic alkylation. Although the allenylation and propargylation of a nucleophile can readily create congested carbon centers, these processes often compete and require careful tuning of substrate structure and reactivity of the nucleophile. The alkenylation/allylic alkylation sequence is a much more studied reactivity mode, which results in the coupling of two nucleophiles. This approach is very popular for the rapid generation of molecular complexity, but also poses several chemo- and regioselectivity issues. These selectivity problems have been traditionally overcome by tethering strategies and cyclization reactions. However, over the past few years, highly selective intermolecular coupling reactions of nucleophiles have also been developed. It is, therefore, unsurprising that, as our prowess to control selectivity has grown, the first methods for the palladium-catalyzed enantioselective installation of quaternary carbon centers with propargylic electrophiles have also appeared.
KW - Palladium catalysis
KW - Propargylic compounds
KW - Quaternary carbon centers
U2 - 10.1016/j.tetlet.2016.06.131
DO - 10.1016/j.tetlet.2016.06.131
M3 - Journal article
VL - 57
SP - 3586
EP - 3595
JO - Tetrahedron Letters
JF - Tetrahedron Letters
SN - 0040-4039
IS - 32
ER -