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(t-Bu)2PN
P(i-BuNCH2CH2)3N: New Efficient Ligand for Palladium-Catalyzed C−N Couplings of Aryl and Heteroaryl Bromides and Chlorides and for Vinyl Bromides at Room Temperature
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Abstract
By employing Pd(OAc)2, Cs2CO3, or NaOH, and the new ligand (t-Bu)2PNP(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (η3-cinnamyl)PdCl·(3a) (5) was also employed successfully in C−N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.
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This article has been cited by 5 ACS Journal articles (5 most recent appear below).
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Oxidative Amination of Heteroaromatic Zinc Reagents Mediated by PhI(OAc)2
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P(PhCH2NCH2CH2)3N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone
Venkat Reddy Chintareddy, Kuldeep Wadhwa and John G. VerkadeThe Journal of Organic Chemistry2009 74 (21), 8118-8132P(PhCH2NCH2CH2)3N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone
Venkat Reddy Chintareddy, Kuldeep Wadhwa and John G. VerkadeThe Journal of Organic Chemistry2009 74 (21), 8118-8132Herein we find that proazaphosphatrane 1c is a very efficient catalyst for Mukaiyama aldol reactions of aldehydes with trimethylsilyl enolates in THF solvent. Only the activated ketone 2,2,2-trifluoroacetophenone underwent clean aldol product formation ...
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History
- Published In Issue April 18, 2008
- Received November 1, 2007
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