99511-86-1Relevant academic research and scientific papers
Synthesis of Optically Active Secondary Allylic Alcohols from Allylsilanes via Successive Asymmetric Dihydroxylation (AD) and Peterson Olefination Reaction
Okamoto, Sentaro,Tani, Kousuke,Sato, Fumie,Sharpless, K. Barry,Zargarian, Davit
, p. 2509 - 2512 (1993)
Optically active, secondary allylic alcohols can be prepared from allylic silanes by the successive asymmetric dihydroxylation and Peterson olefination reactions.The effects of trialkylsilyl groups on the outcome of the AD reaction on vinyl and allyl silanes are also discussed.
Method for preparing chiral gamma-amino alcohol and chiral alpha-allyl alcohol by one-pot method
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Paragraph 0047-0050; 0055; 0204-0214, (2020/12/15)
The invention relates to a method for preparing chiral gamma-amino alcohol and chiral alpha-allyl alcohol by a one-pot method. The method comprises the following steps: making a racemic alpha-allyl alcohol compound, an amine compound, a chiral ruthenium complex and an alkaline reagent react in an organic solvent, and carrying out separation and purification after completion of the reaction, so that chiral gamma-aminoalcohols and chiral alpha-allylalcohol are prepared, wherein a chiral ruthenium complex is selected from one of them. According to the preparation method of the chiral compound, two chiral compounds with wide purposes, namely the chiral gamma-amino alcohol and the chiral alpha-allyl alcohol, are obtained at the same time through a one-pot reaction, the reaction is simple, the atom economy is high, few by-products are produced, and the requirements of green chemistry are met.
A new monooxygenase from: Herbaspirillum huttiense catalyzed highly enantioselective epoxidation of allylbenzenes and allylic alcohols
Lin, Hui,Tang, Yanhong,Dong, Shuang,Lang, Ruibo,Chen, Hongge
, p. 2145 - 2151 (2020/04/17)
Asymmetric epoxidation is a green route to enantiopure epoxides, but often suffers from low enantioselectivity toward unconjugated terminal alkenes. Mining of the NCBI non-redundant protein sequences with a reconstructed ancestral sequence based on six st
Iterative asymmetric allylic substitutions: Syn- and anti-1,2-diols through catalyst control
Park, Jin Kyoon,McQuade, D. Tyler
supporting information; experimental part, p. 2717 - 2721 (2012/04/17)
A copper-catalyzed asymmetric allylic boronation (AAB) gives access to syn- and anti-1,2-diols. The method facilitates an iterative strategy for the preparation of polyols (see scheme), such as the fully differentiated L-ribo-tetrol and protected D-arabin
Highly diastereo- and enantio-selective epoxidation of secondary allylic alcohols catalyzed by styrene monooxygenase
Lin, Hui,Liu, Yan,Wu, Zhong-Liu
supporting information; experimental part, p. 2610 - 2612 (2011/04/26)
Enantiomerically enriched glycidol derivatives with contiguous stereogenic centers were obtained in a highly diastereo- and enantio-selective epoxidation catalyzed with the styrene monooxygenase StyAB2.
Stereoconvergent synthesis of chiral allylboronates from an E/Z mixture of allylic aryl ethers using a 6-NHC-Cu(I) catalyst
Park, Jin Kyoon,Lackey, Hershel H.,Ondrusek, Brian A.,McQuade, D. Tyler
scheme or table, p. 2410 - 2413 (2011/04/25)
We present a 6-NHC-Cu(I) complex that provides α-substituted allylboronates using allylic aryl ether substrates. The method was discovered by comparison of the chemoselectivities exhibited by complexes 1a, 1b, 2, and 3. We observed that 1a preferentially reacts with electron-rich alkenes over electron-deficient alkenes. Development of an asymmetric method revealed that 1b reacts with both the E and Z isomers to provide the same absolute configuration without showing E-Z isomerization. This stereoconvergent reaction occurs with high yields (av 86%), high SN2′ selectivity (>99:1), and high ee (av 94%) and exhibits wide functional-group tolerance using pure E or Z isomer or E/Z alkene mixtures. The stereoconvergent feature enables the use of many different olefination strategies for substrate production, including cross-metathesis. Chiral allylboronates could be purified by silica gel chromatography and stored in the freezer without decomposition.
Ruthenium-catalyzed regio- and enantioselective allylic substitution with water: Direct synthesis of chiral allylic alcohols
Kanbayashi, Naoya,Onitsuka, Kiyotaka
supporting information; experimental part, p. 5197 - 5199 (2011/06/26)
Less is more: A new route to access chiral allylic alcohols through the regio- and enantioselective substitution of monosubstituted allylic chlorides with water has been developed. The reaction is catalyzed effectively by planar-chiral cyclopentadienyl ruthenium complexes (see scheme). Copyright
Chiral a-substituted allylboronates in a one-pot three-component asymmetric allylic alkylation/carbonyl allylation reaction sequence -Applications to the syntheses of (+)-(3R,5R)-3-hydroxy-5-decanolide and (-)-massoialactone
Carosi, Lisa,Hall, Dennis G.
experimental part, p. 650 - 661 (2009/10/30)
The use of different organomagnesium reagents in the copper-catalyzed allylic alkylation of 3-chloropropenyl with chiral phosphoramidite ligands produces the desired a-substituted allylic boronate reagents in high and with modest to high enantioselectivities (up to 96% ee). The size of the incoming alkyl substituent the organomagnesium reagent was found to impact the yield and selectivity of the allylic alkylation. A one-pot for the preparation of these chiral allylic boronates followed by a Lewis acid (BF3) catalyzed addition to aldehydes the desired allylboration products, homoallylic secondary alcohols, in good yields and very high diastereoselectivity.three-component reaction methodology was applied to the syntheses of two lactone-containing natural , (-)-massoialactone and (+)-(3R,5R)-3-hydroxy-5-decanolide. The key step of these syntheses involved the pot enantioselective copper-catalyzed allylic alkylation/allylboration reaction with a benzylic aldehyde, and the desired product in 87% yield, 92% e,and high E/Z selectivity in a ratio of 22:1. Remarkably, the alkylation step of this sequential reaction was performed with a low catalyst loading of 2 mol% on a scale >15 mmol that can provide multiple grams of the three-component product.
Aminocyclopentadienyl Ruthenium Complexes as Racemization Catalysts for Dynamic Kinetic Resolution of Secondary Alcohols at Ambient Temperature
Choi, Jun Ho,Choi, Yoon Kyung,Kim, Yu Hwan,Park, Eun Sil,Kim, Eun Jung,Kim, Mahn-Joo,Park, Jaiwook
, p. 1972 - 1977 (2007/10/03)
Aminocyclopentadienyl ruthenium complexes, which can be used as room-temperature racemization catalysts with lipases in the dynamic kinetic resolution (DKR) of secondary alcohols, were synthesized from cyclopenta-2,4-dienimines, Ru3(CO)12, and CHCl 3: [2,3,4,5-Ph4(η5-C 4CNHR)]Ru-(CO)2Cl (4: R = i-Pr; 5: R = n-Pr; 6: R = t-Bu), [2,5-Me2-3,4-Ph2(η5-C 4CNHR)]Ru(CO)2Cl (7: R = i-Pr; 8: R = Ph), and [2,3,4,5-Ph4(η5-C4CNHAr)]Ru(CO) 2Cl (9: Ar =p-NO2C6H4; 10: Ar = p-ClC6H4; 11: Ar = Ph; 12: Ar = p-OMeC6H 4; 13: Ar = p-NMe2C6H4). The tests in the racemization of (S)-4-phenyl-2-butanol showed that 7 is the most active catalyst, although the difference decreased in the DKR. Complex 4 was used in the DKR of various alcohols; at room temperature, not only simple alcohols but also functionalized ones such as allylic alcohols, alkynyl alcohols, diols, hydroxyl esters, and chlorohydrins were successfully transformed to chiral acetates. In mechanistic studies for the catalytic racemization, ruthenium hydride 14 appeared to be a key species. It was the major organometallic species in the racemization of (S)-1-phenylethanol with 4 and potassium tert-butoxide. In a separate experiment, (S)-1-phenylethanol was racemized catalytically by 14 in the presence of acetophenone.
First synthesis of optically pure selenuranes and stereoselective alkaline hydrolysis. Their application to asymmetric [2,3] sigmatropic rearrangement of allylic selenoxides
Kurose, Noriyuki,Takahashi, Tamiko,Koizumi, Toru
, p. 12115 - 12129 (2007/10/03)
The first synthesis of optically pure selenuranes 1 has been accomplished by utilizing 2-exo-hydroxy-10 bornyl group as a chiral ligand Complete retention of the configuration has been observed in alkaline hydrolysis of 1 to give selenoxides 2. The structure of 1 and 2 has been fully established by X-ray crystallography. [2,3] Sigmatropic rearrangement of allylic selenoxides 2 gave the corresponding allylic alcohols 3 with up to 88% enantiomeric excess (ee). The [2,3] sigmatropic rearrangement of allylic selenoxides 2 progresses predominantly via an endo transition state.
