138713-68-5

Upstream product

• 36206-73-2 (E)-hexa-3,5-dien-1-yl 4-methylbenzenesulfonate 
• 100-46-9 benzylamine 
• 73670-87-8 (E)-hexa-3,5-dien-1-ol 

Downstream Products

• 138713-69-6 4-(benzylhexa-3(E),5-dienylcarbamoyl)-2,3-dihydropyrrole-1-carboxylic acid ethyl ester 
• 265116-03-8 N-benzyl-N-(3E)-3,5-hexadien-1-yl vinylsulfonamide 

Relevant academic research and scientific papers

Domino Acylation/Diels-Alder Synthesis of N -Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions

The development of the domino reaction between an aminoethyl-substituted diene and maleic anhydride to afford an N-substituted octahydroisoquinolin-1-one is described. A typical procedure involves the treatment of a 1-aminoethyl-substituted butadiene with maleic anhydride at 0 C to room temperature for 20 min under low-solvent conditions, which affords a series of isoquinolinone carboxylic acids in moderate to excellent yields. NMR monitoring suggested that the reaction proceeded via an initial acylation step followed by an intramolecular Diels-Alder reaction. For the latter step, a significant rate difference was observed depending on whether the amino group was substituted by a phenyl or an alkyl (usually benzyl) substituent, with the former noted by NMR to be substantially slower. The Diels-Alder step was studied by density functional theory (DFT) methods, leading to the conclusion that the degree of preorganization in the starting acylated intermediate had the largest effect on the reaction barriers. In addition, the effect of electronics on the aromatic ring in N-phenyl substrates was studied computationally and experimentally. Overall, this protocol proved considerably more amenable to scale up compared to earlier methods by eliminating the requirement of microwave batch chemistry for this reaction as well as significantly reducing the quantity of solvent. (Chemical Equation Presented).

SYNTHESIS OF FUNCTIONALIZED OCTAHYDRO-ISOQUINOLIN-1-ONE-8-CARBOXAMIDE, OCTAHYDRO-ISOQUINOLIN-1-ONE-8-CARBOXYLIC ESTERS AND ANALOGS, AND THERAPEUTIC METHODS

A functionalized polycyclic compound can have a structure of Formula 1 or salt, prodrug, analog, or derivative thereof, which compound can be prepared by providing a diene; reacting the diene with a dienophile under sufficient conditions for a combined Diels- Alder/acylation reaction so as to provide a polycyclic compound having a carboxylic acid; and coupling the carboxylic acid with an amine-containing compound or a hydroxyl- containing compound so as to form an amide or an ester and producing a compound having a structure of Formula 1. The compound can be used for modulating an opioid receptor, which can be conducted by administering to an opioid receptor a functionalized polycyclic compound as described herein in an effective amount to modulate the functionality of the opioid receptor. Such opioid modulation can provide a biological benefit to a subject

Enantioselective total syntheses of manzamine A and related alkaloids

As a prelude to undertaking the total syntheses of the complex manzamine alkaloids, a series of model studies were conducted to establish the scope and limitations of intramolecular [4 + 2] cycloadditions of N-acylated vinylogous ureas with the trienic substrates 17a,b, 28a,b, and 34. These experiments clearly demonstrated that the geometry of the internal double bond and the presence of an electron-withdrawing group on the diene moiety were essential for the facile and stereoselective formation of the desired cycloadducts. The enantioselective syntheses of the manzamine alkaloids ircinol A (75), ircinal A (5), and manzamine A (1) were then completed by employing a convergent strategy that featured a novel domino Stille/Diels-Alder reaction to construct the tricyclic ABC ring core embodied in these alkaloids. Thus, the readily accessible chiral dihydropyrrole 58 was first converted in a single chemical operation into the key tricyclic intermediate 60. Two ring-closing metathesis reactions were then used to form the 13- and 8-membered rings leading to Z-72 and 74, the latter of which was quickly elaborated into ircinal A (5) via ircinol A (75). The synthetic 5 thus obtained was converted into manzamine A (1) following literature precedent. This concise synthesis of ircinal A required a total of 24 operations from commercially available starting materials with the longest linear sequence being 21 steps.

High pressure intramolecular Diels-Alder reactions of vinylsulfonates and vinylsulfonamides

Acceleration of the intramolecular Diels-Alder reaction of vinylsulfonic esters and amides bearing acyclic and carbocyclic 1,3-diene moieties by application of high pressure leads to excellent yields of sultones and sultams, respectively, at ambient temperature. The influence of pressure on the stereoselectivity of these processes has been investigated. (C) 2000 Elsevier Science Ltd.

Construction of the tricyclic ABC ring subunit of manzamine A via a novel intramolecular Diels-Alder reaction

A novel entry to the manzamine A (1) has been designed that features an intramolecular Diels-Alder reaction of a vinylogous imide for the facile construction of the tricyclic core of 1 as illustrated by the conversions 8 and 16 → 9.