TY - JOUR
T1 - Palladium-catalysed carboformylation of alkynes using acid chlorides as a dual carbon monoxide and carbon source
AU - Lee, Yong Ho
AU - Denton, Elliott H.
AU - Morandi, Bill
N1 - Funding Information:
We acknowledge ETH Zurich, the European Research Council under the European Union’s Horizon 2020 research and innovation programme (Shuttle Cat, project ID 757608) and LG Chem (fellowship to Y.H.L.) for financial support. We thank the NMR, MS (MoBiAS) and X-ray (SMoCC) service departments at ETH Zurich for technical assistance.
Publisher Copyright:
© 2021, The Author(s), under exclusive licence to Springer Nature Limited.
PY - 2021/2
Y1 - 2021/2
N2 - Hydroformylation, a reaction that installs both a C–H bond and an aldehyde group across an unsaturated substrate, is one of the most important catalytic reactions in both industry and academia. Given the synthetic importance of creating new C–C bonds, the development of carboformylation reactions, wherein a new C–C bond is formed instead of a C–H bond, would bear enormous synthetic potential to rapidly increase molecular complexity in the synthesis of valuable aldehydes. However, the demanding complexity inherent in a four-component reaction, utilizing an exogenous CO source, has made the development of a direct carboformylation reaction a formidable challenge. Here, we describe a palladium-catalysed strategy that uses readily available aroyl chlorides as a carbon electrophile and CO source, in tandem with a sterically congested hydrosilane, to perform a stereoselective carboformylation of alkynes. An extension of this protocol to four chemodivergent carbonylations further highlights the creative opportunity offered by this strategy in carbonylation chemistry. [Figure not available: see fulltext.]
AB - Hydroformylation, a reaction that installs both a C–H bond and an aldehyde group across an unsaturated substrate, is one of the most important catalytic reactions in both industry and academia. Given the synthetic importance of creating new C–C bonds, the development of carboformylation reactions, wherein a new C–C bond is formed instead of a C–H bond, would bear enormous synthetic potential to rapidly increase molecular complexity in the synthesis of valuable aldehydes. However, the demanding complexity inherent in a four-component reaction, utilizing an exogenous CO source, has made the development of a direct carboformylation reaction a formidable challenge. Here, we describe a palladium-catalysed strategy that uses readily available aroyl chlorides as a carbon electrophile and CO source, in tandem with a sterically congested hydrosilane, to perform a stereoselective carboformylation of alkynes. An extension of this protocol to four chemodivergent carbonylations further highlights the creative opportunity offered by this strategy in carbonylation chemistry. [Figure not available: see fulltext.]
UR - http://www.scopus.com/inward/record.url?scp=85099918031&partnerID=8YFLogxK
U2 - 10.1038/s41557-020-00621-x
DO - 10.1038/s41557-020-00621-x
M3 - Article
C2 - 33514937
AN - SCOPUS:85099918031
VL - 13
SP - 123
EP - 130
JO - Nature Chemistry
JF - Nature Chemistry
SN - 1755-4330
IS - 2
ER -