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1 s proceed with a wide variety of ketones and allylic 1,1-diboronate reagents, which enables the effic
2 free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display d
3 is a three-component coupling that joins an allylic acetate, and indole and an organo-B(pin) species
4 ctivity are retained across diverse branched allylic acetates bearing normal alkyl or secondary alkyl
6 ations of racemic branched alkyl-substituted allylic acetates using primary or secondary (hetero)arom
8 re, we report a mechanistic study of aerobic allylic acetoxylation of allylbenzene with a catalyst sy
9 urst phase, involving rapid formation of the allylic acetoxylation product and formation of the dimer
13 hydes and allenes, providing silyl-protected allylic alcohol derivatives possessing a terminal methyl
15 ogical precursor, redox isomerization of the allylic alcohol gave an epimeric mixture of aldehydes, w
17 molecular strategy can overcome the inherent allylic alcohol selectivity of the free catalyst, achiev
18 n-coupled electron transfer activation of an allylic alcohol substrate affords an alkoxy radical inte
20 al beta-alkynyl carbonyl compounds employing allylic alcohol substrates in contrast to more tradition
23 t contain a carboxylic acid, an aldehyde, an allylic alcohol, an aryl olefin, an alpha substituent, o
24 ation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to contro
25 hothiolate complex and afford trisubstituted allylic alcohols and ethers in up to 81% yield and >98%
26 yze the concomitant isomerization of primary allylic alcohols and homoallylboronates into (chiral) al
28 of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions.
33 shed that the isomerization of epoxides into allylic alcohols catalyzed by supported Au nanoparticles
34 ective Markovnikov addition of carbamates to allylic alcohols for the construction of alpha-tertiary
35 ed formal anti-Markovnikov hydroamination of allylic alcohols for the synthesis of chiral gamma-amino
36 formation unravels the unusual reactivity of allylic alcohols in the synthesis of 4-methyleneisochrom
37 zed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of
38 complexes can catalyze the isomerization of allylic alcohols into saturated carbonyl derivatives und
40 s enable the synthesis of either (Z)- or (E)-allylic alcohols regarding the order of introducing coup
41 enantioselective isomerization of secondary allylic alcohols to access ketones with a alpha-tertiary
42 A ferrocenium boronic acid salt activates allylic alcohols to generate transient carbocations that
43 cess, the catalysis allows racemic secondary allylic alcohols to react with various amines, affording
44 ctive arylative semipinacol rearrangement of allylic alcohols using diaryliodonium salts is reported.
46 strate classes, including 4-pentenoic acids, allylic alcohols, homoallyl amines, and bis-homoallylami
49 the development of a Pd-catalyzed asymmetric allylic alkylation (Pd-AAA) of acyclic alpha-hydroxyketo
50 ications in both copper-catalyzed asymmetric allylic alkylation and copper-catalyzed asymmetric boryl
52 ) is designed for catalyzing electrochemical allylic alkylation in water/isopropanol (1:1 v/v) and 0.
53 duction in the inner-sphere asymmetric Tsuji allylic alkylation is C-C bond formation through a seven
55 of a Pd-catalyzed decarboxylative asymmetric allylic alkylation of alpha-nitro allyl esters to afford
56 a challenging palladium-catalyzed asymmetric allylic alkylation of an N-alkyl-alpha,beta-unsaturated
57 Phosferrox (PPh(2)), to palladium catalyzed allylic alkylation of trans-1,3-diphenylallyl acetate re
58 ribe a catalytic, decarboxylative asymmetric allylic alkylation performed on an alpha-silylated subst
59 phosphine ligand facilitate the formation of allylic alkylation products in high branch selectivity.
60 itions for the generation of enantioenriched allylic alkylation products in the presence of catalytic
61 tereo-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to for
62 elective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine l
63 al nucleophiles in a Pd-catalyzed asymmetric allylic alkylation reaction, furnishing phosphinates wit
65 st highly enantioselective iridium-catalyzed allylic alkylation that provides access to products bear
66 n, we report a Cu-catalyzed enantioselective allylic alkylation using a gamma-butyrolactone-derived s
69 re studied in palladium-catalyzed asymmetric allylic alkylations, leading to enantioselectivities fro
70 yzed domino carbopalladation/decarboxylative allylic alkynylation of ortho-iodoallenamides with alkyn
72 that provides access to products bearing an allylic all-carbon quaternary stereogenic center has bee
73 xazole as a vinylogous pronucleophile in the allylic-allylic alkylation of Morita-Baylis-Hillman (MBH
74 (200 mol%) to form the branched products of allylic amination 4a-4l and 5a-5l, respectively, as sing
75 e report the development of a new metal-free allylic amination of alkenes that allows the introductio
76 s undergo alternative oxidative amination or allylic amination pathways, and these reactions will als
78 precedented one-pot successive base-mediated allylic amination/cycloisomerization reaction strategy h
80 cal strategy for the synthesis of high-value allylic amine building blocks that does not require the
83 tereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl
84 The present protocol provides substituted allylic amines in a highly atom- and step-economical man
85 kynes to access alpha,beta,gamma-substituted allylic amines in an atom-economic fashion is reported.
88 nd provides direct access to valuable chiral allylic amines starting from linear or alpha-branched al
90 phos ligand, hydroamination generates chiral allylic amines with high regio- and enantioselectivity.
92 reveal that the cyclization, followed by 1,3-allylic amino dehydroxylation, is preceded by urea forma
93 precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosph
95 catalysts can aminate a variety of benzylic, allylic and aliphatic C-H bonds in excellent enantiosele
97 ture was leveraged to enable fluorination of allylic and benzylic C-H bonds and alpha-C-H bonds of et
98 elective functionalization of less activated allylic and benzylic C-H bonds even in the presence of e
101 eactions to unsaturated carbon-carbon bonds, allylic and propargylic nucleophilic substitutions, C-H
103 s a stereoselective cascade reaction between allylic azides and acrylates that directly generates tet
107 diastereo- and enantioselective synthesis of allylic boronates bearing a Z-trisubstituted alkenyl flu
109 adium-free Stille cross-coupling reaction of allylic bromides and functionalized organostannylfuran u
110 ymmetric alkylation of anthrones with cyclic allylic bromides using quinidine- or quinine-derived cat
111 he lignan scaffold from simple aldehydes and allylic bromides with full control of the two formed ste
113 a sodium amide has been exploited for formal allylic C(sp(3))-H bond activation of alkenes under mild
114 pai bond with the sigma*(CF) orbitals of the allylic C-F bonds results in the increased preference fo
115 al Pd-catalyzed aerobic oxidation reactions: allylic C-H acetoxylation of terminal alkenes and intram
117 he surface OH density and likely involves an allylic C-H activation mechanism, like the molecular W(I
119 t method for intermolecular branch-selective allylic C-H amidation has been accomplished via Ir(III)
123 (CH) coupling constants of the two competing allylic C-H bonds (Delta(1)J(CH)) and the C-H activation
124 system features chemoselective amination of allylic C-H bonds and is compatible with heteroaryl grou
125 s correlated to the electronic properties of allylic C-H bonds indicated by the corresponding (1)J(CH
127 that selectively functionalize benzylic and allylic C-H bonds, affording a broad scope of enantioenr
129 In contrast, initiation of olefins with allylic C-H groups (e.g., beta-methylstyrene) is indepen
130 sis activity toward olefins with and without allylic C-H groups, namely beta-methylstyrene and styren
131 ployed to effect a chemo- and regioselective allylic C-H oxidation in the presence of four oxidizable
132 t of the regioselective Cp*Ir(III)-catalyzed allylic C-H sulfamidation of allylbenzene derivatives, u
133 ore recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streaml
134 ave been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with
138 ion of substituted spiroketals from racemic, allylic carbonates is reported, which enables the instal
139 n of challenging alkyl-substituted secondary allylic carbonates with benzylzinc reagents, which are p
140 he reaction between propargylic alcohols and allylic carbonates, engaging vanadium and palladium cata
141 that increasing the number of deuterated bis-allylic carbons to include both C10 and C13 leads to a m
145 onors and each proceed via cationic species: allylic cations and oxocarbenium ions, respectively.
148 ransfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cl
153 s proceed via stereodefined boron-stabilized allylic Cu species formed by an enantioselective transme
155 er via regioselective acylation, Tsuji-Trost allylic decarboxylative rearrangement, and aromatization
159 ective activation of a single C-F bond in an allylic difluoromethylene group to provide a broad range
162 where we identified 3 new pathways producing allylic epoxide-derived mediators that stimulate regener
163 onic pi-allyl Pd intermediates, derived from allylic ester carbonates and palladium(0) catalyst, were
164 tions occur with alkyl- and aryl-substituted allylic esters and the unstabilized enolates of azaaryl
167 ergo rapid fluoride substitution to generate allylic fluoride products with excellent levels of branc
168 of N-silyl pyrrole latent nucleophiles with allylic fluorides followed by hydrogenation and diastere
170 midates to the corresponding enantioenriched allylic fluorides, via a dynamic kinetic asymmetric tran
171 o found that gamma-, beta-, homoallylic, and allylic fluorination are all possible and predictable th
174 heteroatom stabilization of the intermediate allylic free radical two sites for oxidative product for
179 nal alkenes to be selectively converted into allylic functionalized products with high stereoselectiv
181 l that the azomethine ylide stabilized by an allylic group cycloadds to [60]fullerene in an efficient
182 face-selective reaction of the olefin of the allylic group, leading to a highly diastereoselective fo
183 ing imines, which in turn are susceptible to allylic H-abstraction and further beta-fragmentation lea
184 of alkylzirconocene nucleophiles to racemic allylic halide electrophiles were conducted using a comb
185 elective cross-coupling of alkyl halides and allylic halides to form C-C hydrocarbons with product yi
186 ot observed, while introduction of a second, allylic heteroatom to the substrate results in diminishm
187 turation of aliphatic alcohols into valuable allylic, homoallylic, and bis-homoallylic alcohols has b
188 onates add to glycolaldehyde imine to afford allylic hydroxyl allenes, and allyl boronates add to alk
192 Their stability was attributed to the quasi-allylic interaction of their unpaired electrons with the
193 n of the main scenarios in the generation of allylic intermediates, radical species as formal nucleop
194 nce of a chiral copper catalyst, substituted allylic iodides couple with alpha-diazoesters to generat
196 ienic systems and of the stereocenter at C2 (allylic methine, alpha to the carboxy group) and the pro
197 ctive conjugate addition of boron-stabilized allylic nucleophiles to alpha,beta-unsaturated ketones i
201 lize diverse substrates containing benzylic, allylic or alpha-amino C-H bonds with high turnover and
202 inyldiazonium ions), vinyl carbocations, and allylic or homoallylic carbocation species via vinyldiaz
203 nyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrog
209 oselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a
213 ane family, followed by three site-selective allylic oxidations at C5, C10, and C13, which led to the
214 The successful strategy relied on late-stage allylic oxidations at two separate positions of the mole
216 ve cyclizations of substrates containing a Z-allylic phosphate tethered to an alkyne are described.
217 apid side reaction of a Cu-H complex with an allylic phosphate, while promoting its addition to an al
220 developed reaction conditions where racemic allylic phosphates are suitable substrates using new pho
222 l-, alkenyl-, alkynyl- and alkyl-substituted allylic phosphates may thus be converted to the correspo
223 spectroscopy experiments on reactions using allylic phosphates showed the importance of allyl chlori
225 selective rhodium-catalyzed hydroboration of allylic phosphonates by pinacolborane affords chiral ter
226 More specifically, Z-chloro-substituted allylic pinacolatoboronate is first obtained through ste
227 wide range of nitrogen functionality at the allylic position of alkenes with unique regioselectivity
228 ential replacement of three C-H bonds at the allylic position of propylene and other simple terminal
229 lective installation of benzyl groups at the allylic position to forge tertiary and quaternary carbon
231 enium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an
234 TfOH give rise to reactive conjugated CF(3)-allylic-propargylic cations [Ar-C=C-C(+)(CF(3))-CH=CH-Ar
237 nsition metals as well as the utilization of allylic radical intermediates in beta-functionalization
238 ither delta (Z or E depending on whether the allylic radical is cis or trans) or beta to the OH group
240 rapid intramolecular H(*) transfer, yielding allylic radicals (LZZ + S(*) right arrow over left arrow
243 erve as glycoside mimics that are capable of allylic rather than oxocarbenium cation stabilization.
244 rd reagent, and associated position-specific allylic rearrangement in diastereoselective Pictet-Speng
246 ueezing out the ligand from the conventional allylic S1 binding site, with proton abstraction being a
248 ergo reverse hydroboration reactions to form allylic silanes or can be oxidized to afford highly subs
250 able functionalized allylic systems, such as allylic silanes, boronates, germanes, stannanes, pivalat
252 including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-fre
253 unsaturated fatty acids (PUFAs) at their bis-allylic sites has been identified as a unique approach i
254 eration that reinforces oxidation-prone, bis-allylic sites of PUFAs is a novel, nonantioxidant treatm
255 a silyl cyanide, an alkynyl stannane, and an allylic stannane were applicable to the present reaction
257 cemic allylboronate reagent that contains an allylic stereogenic center, additions were exceptionally
258 d reduction of the hydrazone with an in situ allylic strain controlled retro-ene reaction of an allyl
261 l pincer carbodicarbene ligand that delivers allylic substituted arenes in up to 95% yield and up to
262 f the 'click-to-release' reaction between an allylic substituted trans-cyclooctene linker and a tetra
263 ned Meyer-Schuster rearrangement/Tsuji-Trost allylic substitution clearly illustrates the enormous ad
264 udies of iridium-catalyzed, enantioselective allylic substitution enabled by (phosphoramidite,olefin)
265 e example of a regio- and diastereoselective allylic substitution in the absence of an exogenous liga
266 (2) a catalytic S(N)2'- and enantioselective allylic substitution method involving a mild alkylzinc h
267 io- and diastereoselective rhodium-catalyzed allylic substitution of challenging alkyl-substituted se
268 enophile, and subsequent palladium-catalyzed allylic substitution of the resulting cycloadduct with a
269 uction in an enantioselective intramolecular allylic substitution reaction catalyzed by a combination
270 oned limitations through an interrupted Heck/allylic substitution sequence mediated by visible light.
271 g reaction shows that it involves an initial allylic substitution to form a new Michael acceptor, fol
273 +2]-photocycloaddition that undergoes formal allylic substitution with amine nucleophiles under Pd-ca
275 athway to obtain the latter (aka Tsuji-Trost allylic substitution), metal-catalyzed hydrofunctionaliz
276 treated with oxygen nucleophiles via formal allylic substitution, providing direct access to syn-1,4
277 ) )(2) Lewis acid catalyst system to promote allylic substitution, providing the C2-allylated product
279 kinetically competent to be intermediates in allylic substitutions of branched, racemic allylic alcoh
281 enantioselective transformations, including allylic substitutions, conjugate additions, proto-boryl
282 ropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally sh
284 ery facilitates an ene-cycloisomerization of allylic-sulfide-containing alkenylidenecyclopropanes (AC
285 r selectivity is obtained with both E- and Z-allylic sulfides and the reaction is also feasible with
286 Fusing 1,6-diene with allylic sulfide or allylic sulfone motifs enabled a ring-closing/ring-openi
290 lysis leads to rearomatizing gamma-selective allylic Suzuki-Miyaura cross-coupling to generate 1,1-di
291 enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, ger
295 p and ligand to enable conversion of racemic allylic trichloroacetimidates to the corresponding enant
296 d nucleophilic fluoride source (Et(3)N.3HF), allylic trichloroacetimidates undergo rapid fluoride sub