Enantioselective Synthesis of Tertiary Allylic Fluorides by Iridium‐Catalyzed Allylic Fluoroalkylation
作者:Trevor W. Butcher、John F. Hartwig
DOI:10.1002/anie.201807474
日期:2018.10
Few allylic electrophiles containing two different substituents at a single allyl terminus and none in which one of the two substituents is a heteroatom, have been shown previously to react with iridium catalysts to form substitution products. We report that iridium‐catalysts are uniquely suited to form tertiary allylicfluorides enantioselectively by the addition of a diverse range of carbon‐centered
One-Carbon Homologation of Primary Alcohols to Carboxylic Acids, Esters, and Amides via Mitsunobu Reactions with MAC Reagents
作者:Natsuko Kagawa、Antoinette E. Nibbs、Viresh H. Rawal
DOI:10.1021/acs.orglett.6b00790
日期:2016.5.20
A method is reported for the one-carbon homologation of an alcohol to the extended carboxylic acid, ester, or amide. The process involves the Mitsunobureaction with an alkoxymalononitrile, followed by unmasking in the presence of a suitable nucleophile. The homologation and unmasking can even be performed in a one-pot process in high yield.
Enantioselective Construction of Quaternary Stereogenic Centers by the Addition of an Acyl Anion Equivalent to 1,3-Dienes
作者:Nathan J. Adamson、Sangjune Park、Pengfei Zhou、Andrew L. Nguyen、Steven J. Malcolmson
DOI:10.1021/acs.orglett.0c00412
日期:2020.3.6
We report the enantioselective formation of quaternary stereogenic centers by the intermolecular addition of malononitrile, an acyl anion equivalent, and related pronucleophiles to several 1,3-disubstituted acyclic 1,3-dienes in the presence of a Pd-PHOX catalyst. Products are obtained in up to 88% yield and 99:1 er and in most cases are formed as a single regioisomer. The products' malononitrile unit
Allylation of Carbon Pronucleophiles with Alkynes in the Presence of Palladium/Acetic Acid Catalyst
作者:Nitin T. Patil、Isao Kadota、Akinori Shibuya、Young Soo Gyoung、Yoshinori Yamamoto
DOI:10.1002/adsc.200404046
日期:2004.6
efficient and eco-chemical process for the allylation of carbon pronucleophiles with alkynes. The reaction of alkynes with various active methynes and methylenes in the presence of Pd(PPh3)4/acetic acid gave the corresponding allylated products in high yields and high regioselectivities. In the present catalytic system, the key is the use of carboxylic acid which dramatically enhances the rate of the