Palladium-Catalyzed Carboalkoxylation Research Articles

A convenient synthetic route to furan esters and lactones by palladium-catalyzed carboalkoxylation or cyclocarbonylation of hydroxyl-substituted 3-iodofurans

An effective palladium-catalyzed protocol for the intermolecular carboalkoxylation or intramolecular cyclocarbonylation of hydroxyl-substituted 3-iodofurans under carbon monoxide pressure has been developed. The 3-iodofurans are readily prepared by iodocyclization of 2-(1-alkynyl)-2-alken-1-ones in the presence of various diols.

Facile Synthesis of Alkyl 1-Oxo-3-phenyl-1H-indene-2-carboxylate through Palladium-catalyzed Carboalkoxylation from 2-Bromo-3-phenylinden-1-ones

Abstract Palladium-catalyzed carboalkoxylation of 2-bromo-3-phenylindenones in various alcoholic solvents afforded diverse alkyl 1-oxo-3-phenyl-1H-indene-2-carboxylates in high yields.

Highly Stereoselective Synthesis of (E)‐ and (Z)‐α‐Fluoro‐α,β‐Unsaturated Esters and (E)‐ and (Z)‐α‐Fluoro‐α,β‐Unsaturated Amides from 1‐Bromo‐1‐fluoroalkenes via Palladium‐Catalyzed Carbonylation Reactions.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Highly Stereoselective Synthesis of (E)- and (Z)-α-Fluoro-α,β-unsaturated Esters and (E)- and (Z)-α-Fluoro-α,β-unsaturated Amides from 1-Bromo-1-fluoroalkenes via Palladium-Catalyzed Carbonylation Reactions

The highly stereoselective synthesis of (E)- and (Z)-alpha-fluoro-alpha,beta-unsaturated esters and (E)- and (Z)-alpha-fluoro-alpha,beta-unsaturated amides is described. 1-Bromo-1-fluoroalkenes (E/Z approximately 1:1), which are readily available starting materials, have been found to isomerize to high E/Z ratios after storage at -20 degrees C for 1 week or by photolysis at 254 nm. Since the (E)-isomers have been found to react faster than the corresponding (Z)-isomers at room temperature in Pd(0)-catalyzed reactions, the palladium-catalyzed carboalkoxylation of high E/Z 1-bromo-1-fluoroalkenes lead to a high Z/E (Z/E >/= 98:2) ratio of the alpha-fluoro-alpha,beta-unsaturated esters. When 1-bromo-1-fluoroalkenes (E/Z approximately 1:1) were reacted with HCOOH/NBu(3)/Pd(II)/DMF, the (E)-isomer was selectively reduced, and the remaining (Z)-1-bromo-1-fluoroalkenes were recovered in essentially pure isomeric form. The resulting mixture of (Z)-1-bromo-1-fluoroalkenes and the reduced products underwent similar palladium-catalyzed carboalkoxylation reactions at 70 degrees C, and the (E)-alpha-fluoro-alpha,beta-unsaturated esters were stereospecifically obtained. This methodology was also successfully applied for the stereospecific synthesis of (Z)- and (E)-alpha-fluoro-alpha,beta-unsaturated amides: the palladium-catalyzed carboamidation reaction of high E/Z and (Z)-1-bromo-1-fluoroalkenes lead to pure (Z)- and (E)-alpha-fluoro-alpha,beta-unsaturated amides, respectively.

Indenol ether formation from aryl alkynes bearing ortho-acetals: an unprecedented rearrangement in palladium-catalyzed carboalkoxylation.

Activated ethers: The shown reaction of the dialkylacetals 1 gave the carboalkoxylation products 2 in high to moderate yields. Mechanistic investigation revealed that the reaction proceeded through the addition of an acetal CO bond to the CC triple bond, followed by an unprecedented rearrangement of an alkynyl group substituent.

Kinetic Separation Methodology for the Stereoselective Synthesis of (E)- and (Z)-α-Fluoro-α,β-unsaturated Esters via the Palladium-Catalyzed Carboalkoxylation of 1-Bromo-1-fluoroalkenes

[reaction: see text] Methodology for the stereoselective preparation of both (E)- and (Z)-alpha-fluoro-alpha,beta-unsaturated esters is described. 1-Bromo-1-fluoroalkenes (E/Z approximate 1:1) can be isomerized to high E/Z ratio mixtures, which participate in palladium-catalyzed carboalkoxylation and lead to (Z)-alpha-fluoro-alpha,beta-unsaturated esters in high stereoselectivity. The same starting material can also be kinetically reduced to get an E/Z ratio of 0:100; similar carboalkoxylation reaction at 70 degrees C affords (E)-alpha-fluoro-alpha,beta-unsaturated esters stereospecifically.

An asymmetric synthesis of l-[3- 13C]phenylalanine and l-[3- 13C]tyrosine from [ 13C]carbon monoxide

l-[3- 13C]Phenylalanine and l-[3- 13C]tyrosine were synthesized. [α- 13C]Benzyl bromides were prepared from [ 13C]carbon monoxide via the palladium-catalyzed carboalkoxylation of aryl halides. The asymmetric carbon corresponding to the 2-position in phenylalanine was introduced by the diastereoselective alkylation of Dellaria's oxazinone with [α- 13C]benzyl bromides. Finally, ethanolysis, deprotection, hydrogenolysis and acid hydrolysis of the resulting alkylated oxazinones gave l-[3- 13C]phenylalanine and l-[3- 13C]tyrosine in high optical purity.

ChemInform Abstract: CIR‐FTIR Studies of Palladium‐Catalyzed Carboalkoxylation Reactions

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ChemInform Abstract: PALLADIUM‐CATALYZED CARBOALKOXYLATION OF ARYL, BENZYL, AND VINYLIC HALIDES

Chemischer InformationsdienstVolume 6, Issue 10 Isocyclic Compounds ChemInform Abstract: PALLADIUM-CATALYZED CARBOALKOXYLATION OF ARYL, BENZYL, AND VINYLIC HALIDES A. SCHOENBERG, A. SCHOENBERGSearch for more papers by this authorI. BARTOLETTI, I. BARTOLETTISearch for more papers by this authorR. F. HECK, R. F. HECKSearch for more papers by this author A. SCHOENBERG, A. SCHOENBERGSearch for more papers by this authorI. BARTOLETTI, I. BARTOLETTISearch for more papers by this authorR. F. HECK, R. F. HECKSearch for more papers by this author First published: March 11, 1975 https://doi.org/10.1002/chin.197510187Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume6, Issue10March 11, 1975 RelatedInformation

Palladium-catalyzed carboalkoxylation of aryl, benzyl, and vinylic halides

Palladium-catalyzed carboalkoxylation of aryl, benzyl, and vinylic halides