Efficient and Convenient Palladium‐Catalyzed Amination of Allylic Alcohols with N‐Heterocycles

Banerjee, Debasis; Jagadeesh, Rajenahally V.; Junge, Kathrin; Junge, Henrik; Beller, Matthias

doi:10.1002/ange.201206319

Cited by 35 publications

(5 citation statements)

References 73 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A few methods for allylamine derivatives with amides or electron‐deficient heterocycles are known by applying transition metals or Lewis acids as catalysts, whereby most of these existing methods require large catalyst loadings, high reaction temperature or involve the use of additives for the amination reaction 22…”

Section: Methodsmentioning

confidence: 99%

“…3,4‐Dihydropyrimidinone 1 reacts with paraformaldehyde leading to the formation of acyliminium ion A as a strong electrophile, whose formation is supported by the HR‐MS experimental results ( A was detected at m/z =273, 274 for the reaction of 1a with paraformaldehyde and styrene 2a ). Intermediate A can be stabilized by the conjugation of the carbonyl CO double bond 20b,22. An electrophilic addition of A to the styrene would be preferred because of possible formation of a stable benzallylic species such as B and C , which on subsequent deprotonation should be sterically favoured to afford the thermodynamically controlled ( E )‐type product 3 as the dominant reaction compared to the formation of ( Z )‐type 4 .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

One‐Pot Synthesis of Allylamine Derivatives by Iodine‐ Catalyzed Three‐Component Reaction of N‐Heterocycles, Paraformaldehyde and Styrenes

Quan¹,

Hu²,

Zhang³

et al. 2013

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

One‐Pot Synthesis of Allylamine Derivatives by Iodine‐ Catalyzed Three‐Component Reaction of N‐Heterocycles, Paraformaldehyde and Styrenes

Quan¹,

Hu²,

Zhang³

et al. 2013

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…Based on our continuous interest in transition-metal-catalyzed reactions with CO, [1b] recently we became attracted by carbonylation of allylic compounds, which represents a straightforward and economic method for the synthesis of versatile building blocks, b,g-unsaturated carbonyl compounds. [9f, 10] In line with our previous work on the direct amination of allylic alcohols, [11] we turned our attention to respective carbonylation processes. Most of the reported examples demand preinstalled leaving groups, such as chlorides, [4] carbonates, [5] acetates, [6] or phosphates.…”

mentioning

confidence: 98%

Domino Catalysis: Palladium‐Catalyzed Carbonylation of Allylic Alcohols to β,γ‐Unsaturated Esters

Liu

Jiao

et al. 2013

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

Palladium-catalyzed carbonylations of organic (pseudo)halides are of broad interest for both academic and industrial research. [1] In the last two decades, the majority of the work in this area focused on the application of new ligand systems and the extension of the range of nucleophiles for the carbonylation of aryl and vinyl halides (or related pseudohalides). Consequently, the development of general catalytic protocols for more challenging substrates remains an important but challenging goal. Based on our continuous interest in transition-metal-catalyzed reactions with CO, [1b] recently we became attracted by carbonylation of allylic compounds, which represents a straightforward and economic method for the synthesis of versatile building blocks, b,g-unsaturated carbonyl compounds. [2] In spite of the tremendous progress in nucleophilic allylic substitution reactions, [3] carbonylation of allylic compounds has received much less attention. Most of the reported examples demand preinstalled leaving groups, such as chlorides, [4] carbonates, [5] acetates, [6] or phosphates. [6b,e, 7] Obviously, this creates inherent problems such as significant waste generation and requires less efficient multistep sequences. Moreover, side reactions were observed for carbonylation of allylic halides owing to the accumulation of hydrogen halides in this reaction. However, by adding base to quench the acid, direct reaction with allylic halides is possible. [5a] In general, the resulting b,g-unsaturated carbonyl compounds are highly susceptible to base-catalyzed isomerization, affording a,b-unsaturated carbonyl isomers. [4e] In the well-established carbonylation of allyl alkyl carbonates it is difficult to introduce various nucleophiles owing to the preferred reaction of the alkoxides from the substrates. Besides, allylic carbonates are usually prepared from allylic alcohols and toxic chloroformates. Thus, the overall process is also not really halide-free. Notably, carbonylation reactions of allylic acetates, which are commonly used as electrophiles in Pd-catalyzed allylic substitution reactions, are much less effective. For example, high CO pressure or halide additives are needed. This inefficiency is explained by the formation of p-allylpalladium acetates, which readily undergo reductive elimination to give the starting acetates rather than CO insertion. [8] An ideal way to streamline carbonylation of allylic compounds from an economic and environmental point of view is to use of allylic alcohols directly as substrates. Alcohols are more widely available and represent more environmentally benign reagents, generating water as the sole by-product. Advantageously, the whole synthetic route is shortened because most of the above-mentioned substrates are obtained from the corresponding alcohols. Unfortunately, the poor leaving ability of the hydroxy group, combined with the possible side reactions caused by the released water, have hindered the application of allylic alcohols in carbonylation reactions. [3d] As a result, only ...

show abstract

“…On the basis of our long-standing interest in the catalytic hydroamination of alkynes, [9] and our recent studies on the synthesis of allylic amines by the palladium-catalyzed amination of allylic alcohols, [10] we became interested in the related hydroamidation of 1,3-dienes (Scheme 1). Unfortunately, the use of previous catalyst systems for the hydroamidation of isoprene was not successful.…”

mentioning

confidence: 99%

A General Catalytic Hydroamidation of 1,3‐Dienes: Atom‐Efficient Synthesis of N‐Allyl Heterocycles, Amides, and Sulfonamides

2014

Self Cite

View full text Add to dashboard Cite

Transition-metal-catalyzed hydroamination reactions are sustainable and atom-economical CN bond-forming processes. Although remarkable progress has been made in the inter- and intramolecular amination of olefins and 1,3-dienes, related intermolecular reactions of amides are still much less known. Control of the regioselectivity without analogous telomerization is the particular challenge in the catalytic hydroamidation of alkenes and 1,3-dienes. Herein, we report a general protocol for the hydroamidation of electron-deficient N-heterocyclic amides and sulfonamides with 1,3-dienes and vinyl pyridines in the presence of a catalyst derived from [{Pd(π-cinnamyl)Cl}2 ] and ligand L7 or L10. The reactions proceeded in good to excellent yield with high regioselectivity. The practical utility of our method is demonstrated by the hydroamidation of functionalized biologically active substrates. The high regioselectivity for linear amide products makes the procedure useful for the synthesis of a variety of allylic amides.

show abstract

Efficient and Convenient Palladium‐Catalyzed Amination of Allylic Alcohols with N‐Heterocycles

Cited by 35 publications

References 73 publications

One‐Pot Synthesis of Allylamine Derivatives by Iodine‐ Catalyzed Three‐Component Reaction of N‐Heterocycles, Paraformaldehyde and Styrenes

One‐Pot Synthesis of Allylamine Derivatives by Iodine‐ Catalyzed Three‐Component Reaction of N‐Heterocycles, Paraformaldehyde and Styrenes

Domino Catalysis: Palladium‐Catalyzed Carbonylation of Allylic Alcohols to β,γ‐Unsaturated Esters

A General Catalytic Hydroamidation of 1,3‐Dienes: Atom‐Efficient Synthesis of N‐Allyl Heterocycles, Amides, and Sulfonamides

Contact Info

Product

Resources

About