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1.
《Angewandte Chemie (International ed. in English)》2017,56(16):4612-4616
The treatment of various N‐morpholino amides with TMPZnCl⋅LiCl (TMP=2,2,6,6‐tetramethylpiperidyl) and Mg(OPiv)2 in THF at 25 °C provides solid zinc enolates with enhanced air and moisture stability (t 1/2 in air: 1–3 h) after solvent evaporation. These enolates undergo Pd‐ and Cu‐catalyzed cross‐couplings with (hetero)aryl bromides as well as allylic and benzylic halides. The arylated N‐morpholino amides were converted into various ketones by LaCl3⋅2 LiCl mediated acylation with Grignard reagents. The new, solid enolates were used to prepare a potent anti‐breast‐cancer drug candidate in six steps and 23 % overall yield. 相似文献
2.
Mild Cobalt‐Catalyzed Negishi Cross‐Couplings of (Hetero)arylzinc Reagents with (Hetero)aryl Halides 下载免费PDF全文
M. Sc. Diana Haas M. Sc. Jeffrey M. Hammann B. Sc. Ferdinand H. Lutter Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2016,55(11):3809-3812
A catalytic system consisting of CoCl2 ? 2 LiCl (5 mol %) and HCO2Na (50 mol %) enables the cross‐coupling of various N‐heterocyclic chlorides and bromides as well as aromatic halogenated ketones with various electron‐rich and ‐poor arylzinc reagents. The reactions reached full conversion within a few hours at 25 °C. 相似文献
3.
An efficient synthesis of various α‐halo,α‐allylic aldehydes from α,α‐dihalo ketones using both cyclic (3‐bromocyclohex‐1‐ene zinc bromide and (Z)‐3‐bromocyclobut‐1‐ene zinc bromide) and acyclic (allylzinc bromide and cinnamylzinc bromide) type of allylic organozinc bromide with DMF as base is described. A possible reaction mechanism is also proposed. 相似文献
4.
Synthesis of Branched Alkylboronates by Copper‐Catalyzed Allylic Substitution Reactions of Allylic Chlorides with 1,1‐Diborylalkanes 下载免费PDF全文
Junghoon Kim Sangwoo Park Jinyoung Park Prof. Dr. Seung Hwan Cho 《Angewandte Chemie (International ed. in English)》2016,55(4):1498-1501
Reported herein is a copper‐catalyzed SN2′‐selective allylic substitution reaction using readily accessible allylic chlorides and 1,1‐diborylalkanes, a reaction which proceeds with chemoselective C?B bond activation of the 1,1‐diborylalkanes. In the presence of a catalytic amount of [Cu(IMes)Cl] [IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazole‐2‐ylidene] and LiOtBu as a base, a range of primary and secondary allylic chlorides undergo the SN2′‐selective allylic substitution reaction to produce branched alkylboronates. The synthetic utilities of the obtained alkylboronates are also presented. 相似文献
5.
Generation of Aryl and Heteroaryl Magnesium Reagents in Toluene by Br/Mg or Cl/Mg Exchange 下载免费PDF全文
Dorothée S. Ziegler Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2018,57(22):6701-6704
The alkylmagnesium alkoxide sBuMgOR?LiOR (R=2‐ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR?LiOR) in toluene. These Grignard reagents react with a broad range of electrophiles, including aldehydes, ketones, allyl bromides, acyl chlorides, epoxides, and aziridines, in good yields. Remarkably, the related reagent sBu2Mg?2 LiOR (R=2‐ethylhexyl) undergoes Cl/Mg exchange with various electron‐rich aryl chlorides in toluene, producing diorganomagnesium species of type Ar2Mg?2 LiOR, which react well with aldehydes and allyl bromides. 相似文献
6.
Samir Z. Zard 《Helvetica chimica acta》2012,95(10):1730-1757
The present brief account relates our discovery of new reactions revolving around the chemistry of the NO2 group. It covers the condensation of MeNO2 with hindered ketones, and the synthesis of pyrroles, triazoles, and enamides. It also describes new transformations of allylic nitro compounds, such as their conversion to allylic sulfones and unsaturated lactones, their sigmatropic rearrangement into allylic nitrites and thence into allylic alcohols, as well as their use in a short synthesis of nitroestrone derivatives. This is followed by an unusual reduction method furnishing unsubstituted amines (RR′C?NH) under conditions where these hydrolytically labile species can be captured inter‐ or intramolecularly. Finally, a mechanistic study of a strange alkyne‐forming reaction, first reported by Abidi and later shown by Corey and co‐workers to proceed through allylic nitro intermediates, ultimately led to a practical and powerful synthesis of alkynes starting from β‐keto esters. 相似文献
7.
Triflic acid (TfOH) has been proven to be effective as a tolerant acidic mediator in electrophilic aromatic aroylation with CF3‐bearing aroyl chlorides. The TfOH‐mediated aroylation of fluorobenzene proceeds with high selectivity to give CF3‐bearing aryl fluorophenyl ketones in good yields, which are hardly obtained with the aid of AlCl3 or direct condensation reagents. 相似文献
8.
Isoxazole‐Embedded Allylic Zinc Reagent for the Diastereoselective Preparation of Highly Functionalized Aldol‐Type Derivatives Bearing a Stereocontrolled Quaternary Center 下载免费PDF全文
Lydia Klier Coura R. Diène Manuel Schickinger Albrecht Metzger Andreas J. Wagner Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Ilan Marek Prof. Dr. Paul Knochel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):14096-14101
Highly functionalized aldol‐type products bearing a β‐quaternary center and a stereoselectively controlled γ‐hydroxy function are readily prepared by the diastereoselective addition of an allylic zinc reagent embedded in an isoxazole ring to various aromatic and heteroaromatic aldehydes, in the presence of Lewis acids, such as MgCl2 or LaCl3?2 LiCl. After reductive cleavage of the N?O bond by using Fe, NH4Cl, aldol‐type products bearing a stereocontrolled β‐quaternary center and a γ‐hydroxy group were observed. The benzylic reactivity of the isoxazolylmethylzinc reagent towards other electrophiles, such as acid chlorides, aryl and allylic halides, as well as aldehydes in the presence of BF3?OEt2 are also described. 相似文献
9.
Stereoselective Retentive Domino Transmetalations of Secondary Alkyllithium Compounds to Functionalized Secondary Alkylcopper Reagents 下载免费PDF全文
Kohei Moriya Meike Simon Rasmus Mose Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2015,54(37):10963-10967
Functionalized secondary alkyllithium reagents obtained by I/Li exchange from the corresponding secondary alkyl iodides undergo two successive transmetalations with Me3SiCH2ZnBr?LiBr and CuBr?2 LiCl?Me2S to provide functionalized secondary alkylcopper compounds with high retention of configuration. These alkylcopper derivatives react further with electrophiles such as alkynyl esters, acid chlorides, allylic chlorides, ketals, ethylene oxide, and 3‐iodocyclopentanone with high retention of configuration. A related sequence of transmetalations with MeMgI and LaCl3?2 LiCl allows a retentive addition of secondary alkyllithium reagents to acetone. The influence of the solvent on the configurational stability of secondary alkylzinc reagents is described. 相似文献
10.
Synthesis of Secondary and Tertiary Alkyl Boronic Esters by gem‐Carboborylation: Carbonyl Compounds as Bis(electrophile) Equivalents 下载免费PDF全文
Dunfa Shi Dr. Lu Wang Prof. Dr. Chungu Xia Prof. Dr. Chao Liu 《Angewandte Chemie (International ed. in English)》2018,57(32):10318-10322
An unprecedent gem‐carboborylation of aldehydes and ketones provides access to various secondary and tertiary alkyl boronic esters. The addition of B2pin2 to a carbonyl compound generates α‐oxyl‐substituted alkyl boron species. Organolithium and Grignard reagents are then applied as C nucleophiles for the 1,2‐metalate rearrangement process. The organolithium reagents can also be generated by C?H lithiation or halogen/lithium exchange. The use of chiral ligands led to the generation of chiral alkyl boronic esters in enantioenriched form, demonstrating that the enantioselectivity of this transformation is catalyst‐controlled. 相似文献
11.
Mario Ellwart Dr. Ilya S. Makarov Dr. Florian Achrainer Prof. Dr. Hendrik Zipse Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2016,55(35):10502-10506
Readily prepared allylic zinc halides undergo SN2‐type substitutions with allylic bromides in a 1:1 mixture of THF and DMPU providing 1,5‐dienes regioselectively. The allylic zinc species reacts at the most branched end (γ‐position) of the allylic system furnishing exclusively γ,α′‐allyl–allyl cross‐coupling products. Remarkably, the double bond stereochemistry of the allylic halide is maintained during the cross‐coupling process. Also several functional groups (ester, nitrile) are tolerated. This cross‐coupling of allylic zinc reagents can be extended to propargylic and benzylic halides. DFT calculations show the importance of lithium chloride in this substitution. 相似文献
12.
Dr. Alisa S. Sunagatullina Dr. Andreas Hess Dr. Alexander Kremsmair Yifan Li Yi-Hung Chen Prof. Dr. Paul Knochel 《Angewandte Chemie (International ed. in English)》2023,62(30):e202304445
We reported a new electrophilic amination of various primary, secondary and tertiary alkyl, benzylic, allylic zinc and magnesium organometallics with O-2,4,6-trimethylbenzoyl hydroxylamines (O-TBHAs) in 52–99 % yield. These O-TBHAs displayed an excellent long-term stability and were readily prepared from various highly functionalized secondary amines via a convenient 3 step procedure. The amination reactions showed remarkable chemoselectivity proceeding without any transition-metal catalyst and were usually complete after 1–3 h reaction time at 25 °C. Furthermore, this electrophilic amination also provided access to enantioenriched tertiary amines (up to 88 % ee) by using optically enriched secondary alkylmagnesium reagents of the type s-AlkylMgCH2SiMe3. 相似文献
13.
Construction of Quaternary Stereogenic Carbon Centers through Copper‐Catalyzed Enantioselective Allylic Cross‐Coupling with Alkylboranes 下载免费PDF全文
Kentaro Hojoh Yoshinori Shido Prof. Dr. Hirohisa Ohmiya Prof. Dr. Masaya Sawamura 《Angewandte Chemie (International ed. in English)》2014,53(19):4954-4958
A combination of an in situ generated chiral CuI/DTBM‐MeO‐BIPHEP catalyst system and EtOK enabled the enantioselective SN2′‐type allylic cross‐coupling between alkylborane reagents and γ,γ‐disubstituted primary allyl chlorides with enantiocontrol at a useful level. The reaction generates a stereogenic quaternary carbon center having three sp3‐alkyl groups and a vinyl group. This protocol allowed the use of terminal alkenes as nucleophile precursors, thus representing a formal reductive allylic cross‐coupling of terminal alkenes. A reaction pathway involving addition/elimination of a neutral alkylcopper(I) species with the allyl chloride substrate is proposed. 相似文献
14.
Copper‐Catalyzed Dehydrogenative Cross‐Coupling Reaction between Allylic CH Bonds and α‐CH Bonds of Ketones or Aldehydes 下载免费PDF全文
Xing‐Fen Huang Muhammad Salman Prof. Zhi‐Zhen Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6618-6621
A dehydrogenative cross‐coupling reaction between allylic C?H bonds and the α‐C?H bond of ketones or aldehydes was developed using Cu(OTf)2 as a catalyst and DDQ as an oxidant. This synthetic approach to γ,δ‐unsaturated ketones and aldehydes has the advantages of broad scope for both ketones and aldehydes as reactants, mild reaction conditions, good yields and atom economy. A plausible mechanism using Cu(OTf)2 as a Lewis acid catalyst was also proposed (DDQ=2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone; Tf=trifluoromethanesulfonate). 相似文献
15.
Jiang Wang Brian P. Cary Peyton D. Beyer Samuel H. Gellman Daniel J. Weix 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(35):12209-12213
Synthesis of the C?C bonds of ketones relies upon one high‐availability reagent (carboxylic acids) and one low‐availability reagent (organometallic reagents or alkyl iodides). We demonstrate here a ketone synthesis that couples two different carboxylic acid esters, N‐hydroxyphthalimide esters and S‐2‐pyridyl thioesters, to form aryl alkyl and dialkyl ketones in high yields. The keys to this approach are the use of a nickel catalyst with an electron‐poor bipyridine or terpyridine ligand, a THF/DMA mixed solvent system, and ZnCl2 to enhance the reactivity of the NHP ester. The resulting reaction can be used to form ketones that have previously been difficult to access, such as hindered tertiary/tertiary ketones with strained rings and ketones with α‐heteroatoms. The conditions can be employed in the coupling of complex fragments, including a 20‐mer peptide fragment analog of Exendin(9–39) on solid support. 相似文献
16.
Jiang Wang Brian P. Cary Peyton D. Beyer Samuel H. Gellman Daniel J. Weix 《Angewandte Chemie (International ed. in English)》2019,58(35):12081-12085
Synthesis of the C?C bonds of ketones relies upon one high‐availability reagent (carboxylic acids) and one low‐availability reagent (organometallic reagents or alkyl iodides). We demonstrate here a ketone synthesis that couples two different carboxylic acid esters, N‐hydroxyphthalimide esters and S‐2‐pyridyl thioesters, to form aryl alkyl and dialkyl ketones in high yields. The keys to this approach are the use of a nickel catalyst with an electron‐poor bipyridine or terpyridine ligand, a THF/DMA mixed solvent system, and ZnCl2 to enhance the reactivity of the NHP ester. The resulting reaction can be used to form ketones that have previously been difficult to access, such as hindered tertiary/tertiary ketones with strained rings and ketones with α‐heteroatoms. The conditions can be employed in the coupling of complex fragments, including a 20‐mer peptide fragment analog of Exendin(9–39) on solid support. 相似文献
17.
Reactivity of mixed organozinc and mixed organocopper reagents: 11. Nickel‐catalyzed atom‐economic aryl–allyl coupling of mixed (n‐alkyl)(aryl)zincs 下载免费PDF全文
Melike Kalkan 《应用有机金属化学》2014,28(9):725-732
Group selectivity in the allylation of mixed (n‐butyl)(phenyl)zinc reagent can be controlled by changing reaction parameters. CuCN‐catalyzed allylation in tetrahydrofuran (THF)–hexamethylphosphoric triamide is n‐butyl selective and also γ‐selective in the presence of MgCl2, whereas CuI‐catalyzed allylation in THF in the presence of n‐Bu3P takes place with a n‐butyl transfer:phenyl transfer ratio of 23:77 and an α:γ transfer ratio of phenyl of 76:24. NiCl2(Ph3P)2‐catalyzed allylation in the presence of LiCl is phenyl selective with an α:γ ratio of 65:35. The reaction of methyl‐ or n‐butyl(aryl)zinc reagents with an allylic electrophile in THF at room temperature in the presence of NiCl2(Ph3P)2 catalyst and LiCl as an additive provides an atom‐economic alternative to aryl–allyl coupling using diarylzincs. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
18.
Ruthenium‐Catalyzed Oxidant‐Free Allylation of Aromatic Ketoximes with Allylic Acetates at Room Temperature 下载免费PDF全文
Rajendran Manikandan Padmaja Madasamy Dr. Masilamani Jeganmohan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13934-13938
Substituted aromatic ketoximes reacted efficiently with allylic acetates in the presence of {[RuCl2(p‐cymene)]2} and AgSbF6 in 1,2‐dichloroethane at ambient temperature, providing ortho‐allyl aromatic ketoximes in a highly regioselective manner without an oxidant. In the reaction, the acetate group of allyl acetate acts as a base to activate the C?H bond of aromatics. Later, ortho‐allyl aromatic ketoximes were converted into ortho‐allyl aromatic ketones in the presence of HCl. 相似文献
19.
The catalytic effect of the various butyl-tin chlorides on the dehydrochlorination reaction of chlorohexene, used as a model compound for allylic chlorides in poly(vinyl chloride), has been studied in tetrahydrofuran and dichloroethane solutions. The reaction follows an E2 mechanism, the rate determining step being the formation of a delocalised allylic carbocation. The catalytic power is directly related to the Lewis acidity of the tin chlorides and, further, RSnCl3 is comparable with ZnCl2, although it is more sensitive to complexing with weak Lewis bases. In the presence of poly(vinyl chloride) at 180°C, these butyl-tin chlorides show a retardation effect on dehydrochlorination, superimposed on a catalytic effect which increases with the Lewis acidity; however, in these conditions, RSnCl3 is much less efficient than ZnCl2 in catalysing the dehydrochlorination reaction. 相似文献
20.
Raja A. Sarfraz Tasneem G. Kazi Shahid Iqbal Hassan I. Afridi Mohammad K. Jamali Nusrat Jalbani M. B. Arain 《应用有机金属化学》2008,22(3):187-192
The two new half sandwich amino acids complexes of osmium, i.e. [Os(η6‐p‐cymene)(κ1‐N‐(rac)‐phenylglycine methylester)Cl2] ( A ) and [Os(η6‐p‐cymene)(κ1‐N,N′‐(S)‐phenylalanineamido)Cl] ( B ) have been synthesized and employed for chemoselective reduction of ketones (nine α,β‐unsaturated ketones and three saturated ketones). The complexes were characterized by spectroscopic as well as analytical methods; their solid structures were confirmed by single‐crystal X‐ray analysis. Both of the osmium complexes catalyze the reduction of α,β‐unsaturated ketones to saturated ketones via isomerization of the initially produced allylic alcohols. The reducible substrates were studied to obtain information on the steric and electronic factors which may affect the interaction of the substrate with the metal center and, thus, control the selectivity of the hydrogen‐transfer reductions. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献