37857-30-0

Upstream product

• 153451-37-7 α-methylallylamine hydrochloride 
• 100-39-0 benzyl bromide 
• 100-46-9 benzylamine 
• 6737-11-7 2-acetoxy-3-butene 
• 6117-91-5 (E/Z)-2-buten-1-ol 
• 99268-84-5 but-3-en-2-yl methanesulfonate 
• 536-74-3 phenylacetylene 
• 823785-71-3 (+/-)-3-benzyl-4-methyl-[1,2,3]oxathiazinane-2,2-dioxide 
• 17304-01-7 tricrotylborane 
• 622-79-7 benzyl azide 
• 7204-29-7 trans-2-butenyl acetate 
• 100-52-7 benzaldehyde 
• 50998-70-4 benzaldehyde O-((E/Z)-but-2-enyl)oxime 
• 932-90-1 syn-benzaldehyde oxime 

Relevant academic research and scientific papers

A palladium-catalyst stabilized in the chiral environment of a monoclonal antibody in water

We report the first preparation of a monoclonal antibody (mAb) that can immobilize a palladium (Pd)-complex. The allylic amination reaction using a supramolecular catalyst consisting of the Pd-complex and mAb selectively gives the (R)-enantiomer product w

A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols

The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).

Domino reaction of a gold catalyzed 5-: Endo-dig cyclization and a [3,3]-sigmatropic rearrangement towards polysubstituted pyrazoles

Pyrazoles are important heterocyclic compounds with a broad range of biological activities. A new procedure toward tri- or tetrasubstituted pyrazoles has been developed, via a one-pot gold catalyzed synthesis from hydrazines with alkynyl aldehydes or keto

Synthesis of Cyclic Guanidines Bearing N-Arylsulfonyl and N-Cyano Protecting Groups via Pd-Catalyzed Alkene Carboamination Reactions

Palladium-catalyzed carboamination reactions of N-allylguanidines bearing cleavable N-cyano or N-arylsulfonyl protecting groups are described. The reactions afford cyclic guanidine products in good yield, and transformations of substrates bearing internal alkenes proceed with high diastereoselectivity. Deuterium labeling studies indicate these transformations proceed via anti-aminopalladation pathways.

One-Pot Three-Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination

A synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron-poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium-catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl, and hetereoaryl groups with complete regioselectivity and high diastereoselectivity. The reaction exhibits a high functional-group tolerance. Importantly, either nitrogen atom of the imidazolidine products can be selectively deprotected, while removal of the aminal tether can be achieved in a single step under mild conditions to reveal the free diamine. We expect that this work will promote the further use of mixed aminal tethers in organic synthesis.

Formaldehyde as Tethering Organocatalyst: Highly Diastereoselective Hydroaminations of Allylic Amines

Catalysts possessing sufficient activity to achieve intermolecular alkene hydroaminations under mild conditions are rare, and this likely accounts for the scarcity of asymmetric variants of this reaction. Herein, highly diastereoselective hydroaminations

Palladium-catalyzed vicinal amino alcohols synthesis from allyl amines by in situ tether formation and carboetherification

Vicinal amino alcohols are important structural motifs of bioactive compounds. Reported herein is an efficient method for their synthesis based on the palladium-catalyzed oxy-alkynylation, oxy-arylation, or oxy-vinylation of allylic amines. High regio- and stereoselectivity were ensured through the in situ formation of a hemiaminal tether using the cheap commercially available trifluoroacetaldehyde in its hemiacetal form. The obtained compounds are important building blocks, which can be orthogonally deprotected to give either free alcohols, amines, or terminal alkynes.

Achieving control over the branched/linear selectivity in palladium-catalyzed allylic amination

Palladium-catalyzed reaction of unsymmetrical allylic electrophiles with amines gives rise to regioisomeric allylic amines. We have found that linear products result from the thermodynamically controlled isomerization of the initially formed branched products. The isomerization is promoted by protic acid and active palladium catalyst. The use of base shuts down the isomerization pathway and allows for the preparation and isolation of branched allylic amines. Solvent plays a key role in achieving high kinetic regioselectivity and in controlling the rate of isomerization. The isomerization can be combined with ring-closing metathesis to afford the synthesis of exocyclic allylic amines from their endocyclic precursors.

Hydrogen bonding directed intermolecular cope-type hydroamination of alkenes

Intermolecular hydroamination of unactivated alkenes represents a significant synthetic challenge. An efficient Cope-type hydroamination is achieved under mild conditions for reactions of N-alkylhydroxylamines with allylic amines, using hydrogen bonding t

Hydrogen bonding directed intermolecular cope-type hydroamination of alkenes

Intermolecular hydroamination of unactivated alkenes represents a significant synthetic challenge. An efficient Cope-type hydroamination is achieved under mild conditions for reactions of N-alkylhydroxylamines with allylic amines, using hydrogen bonding t