41285-72-7

Upstream product

• 18402-83-0 (E)-non-3-en-2-one 
• 2548-87-0 (E)-2-Octenal 
• 75-16-1 methylmagnesium bromide 
• 693-25-4 n-pentylmagnesium bromide 
• 2028-63-9 but-3-yn-2-ol 
• 14309-57-0 Non-3-en-2-on 

Downstream Products

• 20063-92-7 (E)-3-nonene 
• 6434-78-2 2-nonene 
• 18402-83-0 (E)-non-3-en-2-one 
• 821-55-6 2-Nonanone 

Relevant academic research and scientific papers

Regioselective oxidation of azidodiols, bromodiols and triol derivatives by dimethyldioxirane

Azidodiols, bromodiols and triol derivatives were regioselectively monooxidised to the corresponding ketols using dimethyldioxirane. This regioselectivity is essentially determined by dipolar functionalities close to the potential reactive carbinol. These results make the reactivity of polyols with dimethyldioxirane highly predictable.

Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones

Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.

Cationic Co(I)-intermediates for hydrofunctionalization reactions: Regio- A nd enantioselective cobalt-catalyzed 1,2-hydroboration of 1,3-dienes

Much of the recent work on catalytic hydroboration of alkenes has focused on simple alkenes and styrene derivatives with few examples of reactions of 1,3-dienes, which have been reported to undergo mostly 1,4-additions to give allylic boronates. We find that reduced cobalt catalysts generated from 1,n-bis-diphenylphosphinoalkane complexes [Ph2P-(CH2)n-PPh2]CoX2; n = 1-5) or from (2-oxazolinyl)phenyldiarylphosphine complexes [(G-PHOX)CoX2] (G = 4-substituent on oxazoline ring) effect selective 1,2-, 1,4-, or 4,3-additions of pinacolborane (HBPin) to a variety of 1,3-dienes depending on the ligands chosen. Conditions have been found to optimize the 1,2-additions. The reactive catalysts can be generated from the cobalt(II)-complexes using trimethylaluminum, methyl aluminoxane, or activated zinc in the presence of sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate (NaBARF). The complex, (dppp)CoCl2, gives the best results (ratio of 1,2-to 1,4-addition >95:5) for a variety of linear terminal 1,3-dienes and 2-substituted 1,3-dienes. The [(PHOX)CoX2] (X = Cl, Br) complexes give mostly 1,4-addition with linear unsubstituted 1,3-dienes, but, surprisingly, selective 1,2-additions with 2-substituted or 2,3-disubstituted 1,3-dienes. Isolated and fully characterized (X-ray crystallography) Co(I)-complexes, (dppp)3Co2Cl2 and [(S,S)-BDPP]3Co2Cl2, do not catalyze the reaction unless activated by a Lewis acid or NaBARF, suggesting a key role for a cationic Co(I) species in the catalytic cycle. Regio- A nd enantioselective 1,2-hydroborations of 2-substituted 1,3-dienes are best accomplished using a catalyst prepared via activation of a chiral phosphinooxazoline-cobalt(II) complex with zinc and NaBARF. A number of common functional groups, among them,-OBn,-OTBS,-OTs, N-phthalimido-groups, are tolerated, and er's > 95:5 are obtained for several dienes including 1-alkenylcycloalk-1-enes. This operationally simple reaction expands the realm of asymmetric hydroboration to provide direct access to a number of nearly enantiopure homoallylic boronates, which are not readily accessible by current methods. The resulting boronates have been converted into the corresponding alcohols, potassium trifluororoborate salts, N-BOC amines, and aryl derivatives by C-BPin to C-aryl transformation.

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.

Studies on the Cu(I)-catalyzed regioselective anti-carbometallation of secondary terminal propargylic alcohols

A highly regioselective Cu(I)-catalyzed anti-carbometallation of secondary terminal propargylic alcohols with 1° alkyl or aryl Grignard reagents affording 2-substituted allylic alcohols was developed. By using this method, optically active allylic alcohols can be prepared from the optically active propargylic alcohols without obvious loss of the enantiopurity. The cyclic organometallic intermediate formed may undergo an iodination or a Pd(0)-catalyzed coupling reaction to afford stereo-defined allylic alcohols.

α,β,γ-trifluoroalkanes: A stereoselective synthesis placing three vicinal fluorines along a hydrocarbon chain

A regio- and stereoselective method for the synthesis of α,β,γ-trifluoroalkanes is described which allows the synthesis of single diastereoisomers of this structural motif. The methodology relied upon regiospecific and stereospecific hydrogen fluoride ring opening of allylic epoxides and then Sharpless cyclic sulfate methodology followed by nucleophilic fluoride attack to introduce the second fluorine. The resultant difluoro alcohol was converted to its triflate which was also displaced by fluoride ion to generate the α,β,γ-trifluoroalkanes. Copyright

Enantioselective Rh-catalyzed hydrogenation of enol acetates and enol carbamates with monodentate phosphoramidites

(Chemical Equation Presented) Monodentate phosphoramidites, in particular PipPhos and its octahydro analogue, are excellent ligands for the rhodium-catalyzed asymmetric hydrogenation of aromatic enol acetates, enol carbamates, and 2-dienol carbamates up to 98% ee. These latter substrates were hydrogenated selectively to the carbamates of the allyl alcohol.

Aminoborohydrides. 4. The Synthesis and Characterization of Lithium Aminoborohydrides: A New Class of Powerful, Selective, Air-Stable Reducing Agents

Lithium aminoborohydrides (LiABH3) are a new class of powerful yet selective reducing agents that reproduce, in air, virtually all of the transformations for which lithium aluminum hydrides is now used.LiABH3's can be readily prepared as solids or generated in situ, are nonpyrophoric, and liberate hydrogen only slowly with protic solvents above pH 4.LiABH3's can be handled in dry air as easily as sodium borohydride and retain their chemical activity for at least 6 month when stored under nitrogen or dry air at 25 deg C.LiABH3's can be synthesized from any primary or secondary amine, thus allowing control of the steric and electronic environment of these reagents.

Aminoborohydrides. 2. Regiospecific reductions of α,β-unsaturated carbonyl compounds with lithium pyrrolidinoborohydride. A facile conversion of α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols in high purity

Lithium aminoborohydrides (LiABH3), obtained by the reaction of n-BuLi with amine-boranes, are powerful reducing agents for the reduction α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols. Thus, lithium pyrrolidinoborohydride (LiPyrrBH3) and reduces cinnamaldehyde and cyclohexenone to give exclusively cinnamyl alcohol and 2-cyclohexen-1-ol respectively. This 1,2-reduction appears to be general and ester groups are tolerated. The yield of allylic alcohols from this procedure is essentially quantitative.