130422-35-4

Upstream product

• 502-44-3 hexahydro-2H-oxepin-2-one 
• 100-46-9 benzylamine 
• 629-11-8 1,6-hexanediol 
• 155193-71-8 5-Hexynoic acid benzylamide 
• 87281-54-7 N-benzylhex-5-enamide 

Downstream Products

• 130422-37-6 5-(Benzylcarbamoyl)pentyl Methanesulfonate 
• 116414-43-8 N-Benzyl-7-(phenylthio)-2-hexahydroazepinone 
• 130422-39-8 N-Benzyl-6-(phenylthio)hexanamide 
• 116436-64-7 N-Benzyl-6-(phenylsulfinyl)hexanamide 
• 133437-08-8 N-benzyl-6-hydroxyhexan-1-amine 

Relevant academic research and scientific papers

Total synthesis, relay synthesis, and structural confirmation of the C18-norditerpenoid alkaloid neofinaconitine

The first total synthesis of the C18-norditerpenoid aconitine alkaloid neofinaconitine and relay syntheses of neofinaconitine and 9-deoxylappaconitine from condelphine are reported. A modular, convergent synthetic approach involves initial Diels-Alder cycloaddition between two unstable components, cyclopropene 10 and cyclopentadiene 11. A second Diels-Alder reaction features the first use of an azepinone dienophile (8), with high diastereofacial selectivity achieved via rational design of siloxydiene component 36 with a sterically demanding bromine substituent. Subsequent Mannich-type N-acyliminium and radical cyclizations provide complete hexacyclic skeleton 33 of the aconitine alkaloids. Key endgame transformations include the installation of the C8-hydroxyl group via conjugate addition of water to a putative strained bridghead enone intermediate 45 and one-carbon oxidative truncation of the C4 side chain to afford racemic neofinaconitine. Complete structural confirmation was provided by a concise relay synthesis of (+)-neofinaconitine and (+)-9-deoxylappaconitine from condelphine, with X-ray crystallographic analysis of the former clarifying the NMR spectral discrepancy between neofinaconitine and delphicrispuline, which were previously assigned identical structures.

Regio- and chemoselective silylmetalation of functionalized terminal alkenes

A regio-/chemoselective silylmetalation of various functionalized alkenes based on the zinc silyl complex in the presence of a catalytic amount of copper cyanide was developed. Silylmetalation of alkenes, followed by electrophilic trapping, proved to be a

Incorporation of primary amines into a polyester chain by a combination of chemical and lipase-catalyzed ε-caprolactone ring-opening processes

A simple chemoenzymatic strategy for the incorporation of bioactive and suitably functionalized molecules into a polyester chain has been developed. The protocol involves first the reaction of a primary amine with ε-caprolactone to give an amide carrying a terminal primary hydroxy group, followed by the enzymatic growth of the polymeric chain triggered by Novozym 435. This method is versatile and easy to handle and is suitable for the incorporationof different amines into polyesters, as has been shown with the model compounds benzylamine and tryptamine, the bioactive compound N-deacetylthiocolchicine and the functionalized propargylamine and tyramine .

Organotin-catalyzed synthesis of hydroxyalkylamides from lactones via a ring-opening process

A new strategy for the facile synthesis of hydroxyalkylamides through the ring-opening reaction of lactone with amine promoted by dibutyltin acetate was developed. A series of hydroxyalkylamide compounds were obtained and the method was successfully applied to the synthesis of pharmaceutically active molecules tyrosinase inhibitor V and HDAC inhibitor VI via a three-step synthetic pathway. The broad substrate scope, mild reaction conditions and practical application proved the effectiveness, compatibility and practicality of this method.

Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes

There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes - often the inspiration for new synthetic transformations - are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades.

A highly active and air-stable ruthenium complex for the ambient temperature anti-markovnikov reductive hydration of terminal alkynes

The conversion of terminal alkynes to functionalized products by the direct addition of heteroatom-based nucleophiles is an important aim in catalysis. We report the design, synthesis, and mechanistic studies of the half-sandwich ruthenium complex 12, which is a highly active catalyst for the anti-Markovnikov reductive hydration of alkynes. The key design element of 12 involves a tridentate nitrogen-based ligand that contains a hemilabile 3-(dimethylamino) propyl substituent. Under neutral conditions, the dimethylamino substituent coordinates to the ruthenium center to generate an air-stable, 18-electron, κ3-complex. Mechanistic studies show that the dimethylamino substituent is partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate aldehyde, operate concurrently in reactions mediated by 12. A wide array of terminal alkynes are efficiently processed to linear alcohols using as little as 2 mol % of 12 at ambient temperature, and the complex 12 is stable for at least two weeks under air. The studies outlined herein establish 12 as the most active and practical catalyst for anti-Markovnikov reductive hydration discovered to date, define the structural parameters of 12 underlying its activity and stability, and delineate design strategies for synthesis of other multifunctional catalysts.

Regioselective reductive hydration of alkynes to form branched or linear alcohols

The regioselective reductive hydration of terminal alkynes using two complementary dual catalytic systems is described. Branched or linear alcohols are obtained in 75-96% yield with ?25:1 regioselectivity from the same starting materials. The method is compatible with terminal, di-, and trisubstituted alkenes. This reductive hydration constitutes a strategic surrogate to alkene oxyfunctionalization and may be of utility in multistep settings.

Reductive hydroxyalkylation/alkylation of amines with lactones/esters

We have developed a one-pot method for the direct intermolecular reductive hydroxyalkylation or alkylation of amines using lactones or esters as the hydroxyalkylating/alkylating reagents. The method is based on the in situ amidation of lactones/esters with DIBAL-H-amine complex (for primary amines) or DIBAL-H-amine hydrochloride salt complex (for secondary amines), followed by reduction of the amides with an excess of DIBAL-H. Different from the reduction of Weinreb amides with DIBAL-H where aldehydes are formed, the reduction of the in situ formed Weinreb amides yielded amines. Moreover, this method is not limited to Weinreb amides, instead, it also works for other amides in general. A plausible mechanism is suggested to account for the outcome of the reactions.