58649-21-1

Upstream product

• 4352-44-7 1-cyclohexylprop-2-en-1-ol 
• 2043-61-0 cyclohexanecarbaldehyde 
• 1826-67-1 vinyl magnesium bromide 
• 42134-55-4 (E)-3-cyclohexyl-2-propen-1-ol 
• 42134-55-4 (Z)-3-cyclohexyl-2-propene-1-ol 
• 17343-88-3 (E)-3-cyclohexyl-acrylic acid ethyl ester 

Downstream Products

• 91899-33-1 <(E)-3-(Trimethylsilyl)-1-propenyl>-cyclohexane 
• 91899-32-0 3-cyclohexyl-3-trimethylsilyl-1-propene 
• 125847-56-5 (R)-(but-3-en-2-yl)cyclohexane 
• 1172595-23-1 (E)-(3-cyclohexylallyl)(phenyl)sulfane 
• 1334681-05-8 C₉H₁₅F 
• 1334680-88-4 (S)-(1-fluoroallyl)cyclohexane 
• 1427549-15-2 (S)-2-(4-cyclohexylhexa-1,5-dien-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1237786-79-6 (S)-hexa-1,5-dien-3-ylcyclohexane 
• 103499-84-9 (2E)-1-cyano-3-cyclohexyl-2-propene 
• 135987-59-6 1-cyclohexylheptene 
• 1262617-01-5 3-(cyclohexylmethylene)-2,3-dihydro-4H-1-benzopyran-4-one 

Relevant academic research and scientific papers

Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement

A gold(I)-catalyzed enantioselective thioallylation of propiolates with allyl sulfides is described. The key mechanistic element is a sulfonium-induced Claisen rearrangement which helps minimize the allyl dissociation and render higher enantioselectivity. This protocol features remarkable scope of the allyl moiety, allowing enantiocontrolled synthesis of all-carbon quaternary centers, and exhibits exceptional functional group compatibility with many Lewis bases and π-bonds. This intermolecular variant of Claisen rearrangement forges both C-S and C-C bonds concomitantly, providing efficient access to interesting optically active organosulfur compounds which can be transformed further through the vinyl sulfide as a functional handle. The rate of the reaction was zeroth order with respect to allyl sulfides, which suggested a reversible inhibition, providing a resting state for the catalyst. The Hammett plot displayed a correlation with σp values, suggesting a turnover-limiting sigmatropic rearrangement where decreased electron-density on sulfur accelerated the rearrangement.

A Convenient Palladium-Catalyzed Carbonylative Synthesis of (E)-3-Benzylidenechroman-4-ones

A convenient palladium-catalyzed carbonylation reaction for the efficient synthesis of (E)-3-benzylidenechroman-4-ones has been developed. Using TFBen as a solid CO source, a range of substituted (E)-3-benzylidenechroman-4-ones were prepared in moderate to good yields with 2-iodophenols and allyl chlorides as the substrates. Additionally, substituted quinolin-4(1H)-ones can also be obtained with 2-iodoaniline as the starting material.

Rhodium(ii)-catalyzed intramolecular formal [4 + 3] cycloadditions of dienyltriazoles: Rapid access to fused 2,5-dihydroazepines

Rhodium(ii)-catalyzed intramolecular [4 + 3] cycloadditions of dienyltriazoles have been developed, which enable the efficient synthesis of various fused 2,5-dihydroazepines. Mechanistically, the titled reaction proceeds via an interesting tandem cyclopropanation/aza-cope rearrangement.

Catalytic enantioselective allyl-allyl cross-coupling with a borylated allylboronate

Catalytic enantioselective allyl-allyl cross-coupling of a borylated allylboronate reagent gives versatile borylated chiral 1,5-hexadienes. These compounds may be manipulated in a number of useful ways to give functionalized chiral building blocks for asymmetric synthesis.

Palladium-catalyzed regio- and enantioselective fluorination of acyclic allylic halides

This report describes the Pd(0)-catalyzed fluorination of linear allylic chlorides and bromides, yielding branched allylic fluorides in high selectivity. Many of the significant synthetic limitations previously associated with the preparation of these products are overcome by this catalytic method. We also demonstrate that a chiral bisphosphine-ligated palladium catalyst enables highly enantioselective access to a class of branched allylic fluorides that can be readily diversified to valuable fluorinated products.

Application of a chiral scaffolding ligand in catalytic enantioselective hydroformylation

The synthesis of β-amino-aldehydes has been achieved through enantioselective hydroformylation of PMP-protected allylic amines. The reaction is accomplished by using a scalemic scaffolding ligand that covalently and reversibly binds to the substrate. These ligands behave like chiral auxiliaries because they are covalently attached to the substrate during hydroformylation; however, similar to traditional asymmetric ligands, they can be used in catalytic quantities. The directed hydroformylation of disubstituted olefins occurs under mild conditions (35 °C and 50 psi CO/H2), and Z-olefins afford excellent enantioselectivities (up to 93% ee).

Expedient access to branched allylic silanes by copper-catalysed allylic substitution of linear allylic halides

An unprecedented copper-catalysed allylic transposition enables the regioselective synthesis of branched allylic silanes from linear allylic halides through direct C-Si bond formation.

Allylic and allenic halide synthesis via NbCl5- and NbBr 5-mediated alkoxide rearrangements

(Chemical Equation Presented) Addition of NbCl5 or NbBr 5 to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metallahalo-[3,3] rearrangement, although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure (E)-allylic or -allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. 2009 American Chemical Society.

Direct conversion of aldehydes and ketones to allylic halides by a NbX 5-[3,3] rearrangement

Sequential addition of vinylmagnesium bromide and NbCl5, or NbBr5, to a series of aldehydes and ketones directly provides homologated, allylic halides. Transposition of the intermediate vinyl alkoxide is envisaged through a metalo-halo-[3,3] rearrangement with concomitant delivery of the halogen to the terminal carbon. The [3,3] rearrangement is equally effective for the conversion of a propargyllic alcohol to the corresponding allenyl bromide. Georg Thieme Verlag Stuttgart.

One-pot formation of allylic chlorides from carbonyl derivatives

(Chemical Equation Presented) An efficient, one-pot method for the conversion of carbonyl electrophiles to allylic chlorides has been developed, by activating magnesium alkoxides in situ using TiCl4.