35666-69-4

Upstream product

• 42537-25-7 phthalic acid mono-((S)-1-methyl-but-2t-enyl ester) 
• 100312-77-4 tert-Butyl-dimethyl-((E)-(S)-1-methyl-but-2-enyloxy)-silane 
• 1569-50-2 3-penten-2-ol 
• 85217-71-6 methyl (3E)-pent-3-en-2-yl carbonate 
• 67-56-1 methanol 
• 819852-45-4 C₁₀H₁₃BrOSSe 
• 31001-80-6 3-penten-2-yl acetate 
• 22468-74-2 Dodecanoic acid (E)-1-methyl-but-2-enyl ester 
• 24652-50-4 (Z)-pent-3-en-2-ol 
• 27301-54-8 (S)-(+)-pent-3-yn-2-ol 
• 1126011-07-1 (2S,3Z)-2-(tetrahydropyranyloxy)pent-3-ene 
• 95482-82-9 (E)-(R)-1-((R)-Toluene-4-sulfinyl)-pent-3-en-2-ol 
• 57984-70-0 Pent-3-yn-2-ol 
• 131573-41-6 (2S,3S,4S)-2-(tert-Butyl-dimethyl-silanyloxy)-4-(diphenyl-phosphinoyl)-pentan-3-ol 

Downstream Products

• 854260-37-0 ((pent-3-en-2-yloxy)methyl)benzene 
• 940-39-6 D-4-phenoxy-pent-2t-ene 
• 26184-62-3 (S)-2-pentanol 
• 27125-91-3 4-Methoxy-2-penten 
• 200723-19-9 (R,E)-1,2,3-trimethyl-5-(pent-3-en-2-yloxy)benzene 
• 1202792-73-1 (2S,3R,E)-methyl 2-hydroxy-3-methyl-2-phenylhex-4-enoate 
• 1384062-83-2 (2R,3R,E)-methyl 2-hydroxy-3-methyl-2-((E)-styryl)hex-4-enoate 
• 1384062-87-6 (2S,3R,E)-methyl 2-(4-bromophenyl)-2-hydroxy-3-methylhex-4-enoate 
• 1384062-88-7 (2R,3R,E)-methyl 2-((E)-4-bromostyryl)-2-hydroxy-3-methylhex-4-enoate 
• 1373874-51-1 (R,E)-3-methyl-1-phenylhex-4-en-3-ol 
• 1373874-52-2 (R,E)-2-cyclohexylpent-3-en-2-ol 
• 1373874-53-3 (S,E)-2-phenylpent-3-en-2-ol 
• 182965-24-8 (Z)-4-hydroxypent-2-en-2-yl diisopropylcarbamate 

Relevant academic research and scientific papers

Total synthesis of (+)-rubriflordilactone A

Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium- or cobalt-catalyzed cyclizations to form the CDE rings, and converge on a late-stage synthetic intermediate. These key processes are set up through the convergent coupling of a common diyne component with appropriate AB-ring aldehydes, a strategy that sets the stage for the synthetic exploration of other members of this family of natural products. Two in one: Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium- or cobalt-catalyzed cyclizations to converge on a late-stage synthetic intermediate. These key processes are set up through the coupling of a common diyne component with appropriate AB-ring aldehydes, a strategy that enables a broad exploration of this family of natural products, as well as synthetic analogues.

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that Erode the efficiency of chirality transfer become competitive.

Highly stereoselective C-C bond formation by rhodium-catalyzed tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor carbenoids and chiral allylic alcohols

The tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor rhodium carbenoids and chiral allyl alcohols is a convergent C-C bond forming process, which generates two vicinal stereogenic centers. Any of the four possible stereoisomers can be selectively synthesized by appropriate combination of the chiral catalyst Rh2(DOSP)4 and the chiral alcohol.

Palladium(II)-catalyzed dicarboxymethylation of chiral allylic alcohols: Chirality transfer affording optically active diesters containing three contiguous chiral centers

This manuscript describes the extension of Stille's palladium-catalyzed olefin dicarbonylation reaction to chiral allylic alcohols with chirality transfer to afford the corresponding chiral alcohol functionalized with bis-carbomethoxy esters, containing three contiguous chiral centers, in good to excellent diastereoselectivities (78-98%).

Synthesis of the active form of loxoprofen by using allylic substitutions in two steps

High regioselectivity for allylic substitution of the cyclopentenyl picolinate 5 with benzylcopper reagent was attained with ZnBr2, and the finding was applied to the p-BrC6H4CH2 reagent. The cyclopentene moiety in the product was reduced to the cyclopentane, and the p-BrC6H4 was converted to the "Cu"C6H4 for the second allylic substitution with picolinate 8 to furnish the title compound after oxidative cleavage of the resulting olefin moiety.

A synthetic approach toward nitiol: Construction of two 1,22-dihydroxynitianes

Synthetic work toward the total synthesis of nitiol has culminated in the construction of two epimeric hydroxylated derivatives, the 1,22- dihydroxynitianes. Key stereodefining steps in the construction of the A-ring fragment (13) were the use of a siloxy-epoxide rearrangement reaction, a Pauson-Khand reaction, a Norrish 1 photochemical cleavage reaction, and a highly regio- and stereoselective hydrostannylation reaction of an ynoate. The stereochemistry of the synthetically challenging C-ring fragment (20) was established using an Ireland-Claisen reaction and a Grubbs ring-closing metathesis process as key steps. The 12-membered B-ring of the nitiane skeleton was constructed using a copper-promoted Stille cross-coupling and a Kishi-Hiyama-Nozaki carbonyl addition reaction. Unfortunately, the carbonyl addition reaction produced hydroxyl functionality that could not be selectively removed. Consequently, a synthesis of epimeric 1,22-dihydroxynitianes, which are compounds that are structural hybrids of two natural products, nitiol and variculanol, was completed.

Palladium-catalyzed asymmetric synthesis of allylic alcohols from unsymmetrical and symmetrical racemic allylic carbonates featuring C-O-bond formation and dynamic kinetic resolution

Described is the asymmetric synthesis of the allylic alcohols 11 (85% ee), 15 (99% ee), 17 (93% ee), 19 (61% ee), and 21 (69% ee) through a Pd-catalyzed reaction of the unsymmetrical carbonates rac-10, rac-12, rac-14, rac-16, rac-18, and rac-20, respectively, with KHCO3 and H2O in the presence of bisphosphane 6. Similarly the allylic alcohols 23 (99% ee) and 25 (97% ee) have been obtained from the symmetrical carbonates rac-22 and rac-24, respectively. Reaction of the meso-biscarbonate 26 with H2O and Pd(0)/6 afforded alcohol 27 (96% ee), which was converted to the PG building block 32. The unsaturated bisphosphane 33 showed in the synthesis of alcohols 36, 37, and 39 a similar high selectivity as 6. The formation of alcohols 11, 15, and 17 involves an efficient dynamic kinetic resolution.

A chiral electrophilic selenium reagent to promote the kinetic resolution of racemic allylic alcohols

(Chemical Equation Presented) The first example of a kinetic resolution process promoted by electrophilic selenium reagents is reported. Racemic allylic alcohols react with half equivalents of a selenenylating agent in methanol leading to the regiospecific formation of the corresponding addition products with a very high level of facial selectivity (from 95:5 to 98:2 dr). The unreacted alcohols can be recovered in an optically enriched form (from 90 to 94% ee).

Palladium-catalyzed deracemization of allylic carbonates in water with formation of allylic alcohols: Hydrogen carbonate ion as nucleophile in the palladium-catalyzed allylic substitution and kinetic resolution

The palladium-catalyzed deracemization of racemic cyclic and acyclic allylic methyl carbonates in water in the presence of N,N′-(1R,2R)-1,2-cyclohexanediylbis[2-(diphenylphophino)benzamide] proceeds with high enantioselectivities to give the corresponding allylic alcohols in high yields. This deracemization involves a palladium-catalyzed allylic substitution with the in-situ-formed hydrogen carbonate ion and an irreversible decomposition of the intermediate allylic hydrogen carbonates, with formation of the corresponding allylic alcohols. The palladium-catalyzed reaction of racemic cyclic allylic acetates with potassium hydrogen carbonate in water in the presence of the chiral bisphosphane proceeds with a highly selective kinetic resolution to give the corresponding allylic alcohols and allylic acetates. Copyright