61307-73-1

Usage

Uses

Used in Fragrance Industry:
Lilial is used as a scent additive for its floral, lily of the valley-like aroma, enhancing the olfactory experience of perfumes, soaps, and lotions.
Used in Cosmetic Industry:
In the cosmetic industry, Lilial serves as a fragrance ingredient, providing a fresh and floral scent to a range of products, thereby improving consumer appeal.
However, it is important to note that Lilial has been identified as a common allergen in skincare products, which can lead to skin sensitization and irritation in some individuals. As a result of its potential health risks, there has been increased regulation and restriction of its use within the European Union. The industry is progressively moving towards the adoption of safer alternatives to Lilial in order to mitigate these risks and ensure consumer safety.

Upstream product

• 173198-20-4 1-(4'-tert-butylphenyl)-1-methyloxirane 
• 943-27-1 4'-t-butylacetophenone 
• 25163-88-6 2-(4-tert-butylphenyl)propene 
• 50-00-0 formaldehyd 
• 1746-23-2 4-tert-Butylstyrene 
• 201230-82-2 carbon monoxide 

Downstream Products

• 135055-78-6 (R)-(+)-2-<(4-tert-Butylphenyl)methyl>-2-methyl-2-pentenal 
• 135055-78-6 (S)-2-<(4-tert-Butylphenyl)methyl>-2-methyl-2-pentenal 

Relevant academic research and scientific papers

Palladium-Catalyzed Allenamide Carbopalladation/Allylation with Active Methine Compounds

A palladium-catalyzed allenamide carbopalladation/allylation with active methine compounds has been developed. Various indoles and isoquinolinones bearing a quaternary carbon center were achieved with good efficiency, a broad substrate scope and good functional group tolerance. This reaction underwent cascade oxidative addition, carbopalladation, and allylic alkylation, and two new C-C bonds were formed in one pot.

Copper-catalyzed hydroformylation and hydroxymethylation of styrenes

Hydroformylation catalyzed by transition metals is one of the most important homogeneously catalyzed reactions in industrial organic chemistry. Millions of tons of aldehydes and related chemicals are produced by this transformation annually. However, most of the applied procedures use rhodium catalysts. In the procedure described here, a copper-catalyzed hydroformylation of alkenes has been realized. Remarkably, by using a different copper precursor, the aldehydes obtained can be further hydrogenated to give the corresponding alcohols under the same conditions, formally named as hydroxymethylation of alkenes. Under pressure of syngas, various aldehydes and alcohols can be produced from alkenes with copper as the only catalyst, in excellent regioselectivity. Additionally, an all-carbon quaternary center containing ethers and formates can be synthesized as well with the addition of unactivated alkyl halides. A possible reaction pathway is proposed based on our results. This journal is

Synthesis of rac-ɑ-aryl propionaldehydes via branched-selective hydroformylation of terminal arylalkenes using water-soluble Rh-PNP catalyst

This work detailed the preparation of a class of water-soluble PNP ligands that differed by the nature of the substitute on phenyl ring of ligands. These ligands were incorporated into water-soluble rhodium-PNP complex catalysts that were used to regioselective hydroformylation of a series of terminal arylalkenes, providing efficient access to rac-α-aryl propionaldehydes in good to excellent yield (up to 97%) and branched-regioselectivity (up to 40:1 b/l ratio). Furthermore, gram-scale and diverse synthetic transformation demonstrated synthetic application of this methodology for non-steroidal antiinflammatory drugs.

Organic Ligand-Free Hydroformylation with Rh Particles as Catalyst?

An efficient and organic ligand-free heterogeneous catalytic system for hydroformylation of olefins is highly desirable for both academy and industry. In this study, simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in the absence of organic ligand. The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic olefins, affording the desired aldehydes in good yields. Taking the hydroformylation of ethylene as an example, 86% yield of propanal and TOF of 200 h–1 were obtained, which was superior to the reported homogeneous catalytic systems. In addition, the catalyst could be reused five times without loss of activity under identical reaction conditions, and the Rh leaching was negligible after each cycle.

Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes

Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.

Rhodium-catalyzed asymmetric hydrogenation of β-branched enamides for the synthesis of β-stereogenic amines

Using a rhodium complex of a bisphosphine ligand (R)-SDP, β-branched simple enamides with a (Z)-configuration were hydrogenated to β-stereogenic amines in quantitative yields and with excellent enantioselectivities (88-96% ee).

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)4]-[Ph3PNPPh3]+ (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)2(PPh3)2] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.

Calix[4]arene-fused phospholes

An upper rim, o-(diphenylphosphinyl)phenyl-substituted calix[4]arene has been prepared and its coordinative properties investigated. When heated in the presence of palladium, the new biarylphosphine undergoes conversion into two diastereomeric, calixarene-fused phospholes. In both, the P lone pair adopts a fixed orientation with respect to the calixarene core. The more hindered phosphole (8), i.e. the one with the endo-oriented lone pair (cone angle 150°-175°), forms complexes having their metal centre positioned very near the calixarene unit but outside the cavity, thus inducing an unusual chemical shift of one of the methylenic ArCH2Ar protons owing to interactions with the metal centre. As expected for dibenzophospholes, the complex [Rh(acac)(CO)·8], when combined with one equivalent of free 8, efficiently catalyses the hydroformylation of styrene, the catalytic system displaying high regioselectivity in favour of the branched aldehyde (b/l ratio up to 30). The optical and redox properties of the derivatives have also been investigated.

Coordination of bis(azol-1-yl)methane-based bisphosphines towards RuII, RhI, PdII and PtII: synthesis, structural and catalytic studies

The coordination chemistry of bisphosphine ligands assembled on the five-membered heterocyclic platform of bis(azol-1-yl)methane viz.: bis(2-diphenylphosphinoimidazol-1-yl)methane (1), bis(5-diphenylphosphinopyrazol-1-yl)methane (2) and bis(5-diphenylphosphino-1,2,4-triazol-1-yl)methane (3) with RuII, RhI, PdII and PtII is described. The bisphosphines 1-3 react with elemental selenium to give the corresponding bis-selenoyl derivatives 4-6. The reactions of 1-3 with transition metal derivatives produce complexes with different coordination modes. Bisphosphine 1 showed a preference for the κ2-P,P mode of coordination, whereas bisphosphines 2 and 3, besides the κ2-P,P mode also showed a head-to-tail κ2-P,N coordination mode resulting in the formation of binuclear complexes [Rh2(COD)2{(CH2(1,2-C3H2N2PPh2)2)-κ2P,N}][BF4]2 (14), [Rh2(COD)2{(CH2(1,2,4-C2HN3PPh2)2)-κ2P,N}][BF4]2 (15), [Pd2(η3-C3H5)2{(CH2(1,2-C3H2N2PPh2)2)-κ2P,N}][BF4]2 (21) and [Pd2(η3-C3H5)2{(CH2(1,2,4-C2HN3PPh2)2)-κ2P,N}][BF4]2 (22). Several of these complexes have also been structurally characterized. The in situ generated RhI complex of bisphosphine 1 showed moderate to good selectivity in the hydroformylation of various styrene derivatives.

Bisamino(diphosphonite) with dangling olefin functionalities: Synthesis, metal chemistry and catalytic utility of Rhi and Pdii complexes in hydroformylation and Suzuki-Miyaura reactions

Bisamino(diphosphonite), p-C6H4{N{P(OC 6H4C3H5-o)2} 2}2 (1), was prepared by reacting p-C6H 4{N(PCl2)2}2 with four equivalents of o-allylphenol in 85% yield. Compound 1 on treatment with [M(CO) 4(HNC5H10)2] (M = Mo or W) gave cis-[{M(CO)4}2{p-C6H4{N(P(OC 6H4C3H5-o)2) 2}2}] (2, M = Mo; 3, M = W). The reaction of 1 with [Fe(η5-C5H5)(CO)2]2 yielded the complex [{Fe(η5-C5H5)(μ-CO)} 2{p-C6H4{N(P(OC6H4C 3H5-o)2)2}2}] (4). Treatment of 1 with Fe(CO)5 furnished a mononuclear complex, [{Fe(CO)3}2{p-C6H4{N{P(OC 6H4C3H5-o)2} 2}2}] (5). The ruthenium(ii) complex, [{(η 6-p-cymene)Ru(μ-Cl)3RuCl}2{p-C 6H4{N(P(OC6H4C3H 5-o)2)2}2}] (6), was obtained on treatment of ligand 1 with [(η6-p-cymene)Ru(Cl)2] 2. The reaction between 1 and [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) in dichloromethane resulted in the formation of a dinuclear complex [{RhCl}2{p-C6H4{N(P(OC 6H4C3H5-o)2) 2}2}] (7), in which the allyl double bond of one of the phenoxy groups coordinates to the metal center. When ligand 1 was reacted with two equivalents of [Pd(COD)Cl2], a dinuclear complex [{PdCl 2}2{p-C6H4{N(P(OC6H 4C3H5-o)2)2} 2}] (8) was obtained. With copper(i) halides, ligand 1 afforded tetranuclear complexes, [{(Cu(μ-X)(NCCH3))2} 2{p-C6H4{N(P(OC6H4C 3H5-o)2)2}2}] (9, X = Cl; 10, X = Br; 11, X = I). Reaction of 1 with four equivalents of [AuCl(SMe 2)] produced a tetranuclear complex, [(AuCl)4{p-C 6H4{N{P(OC6H4C3H 5-o)2}2}2}] (12). Complex 8 shows excellent catalytic activity in the Suzuki-Miyaura cross-coupling reaction under microwave conditions and complex 7 catalyzes hydroformylation of styrenes with good TONs. The Royal Society of Chemistry 2014.