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1 cyclization step is found to be governed by allylic 1,2-strain arising from the interaction of the N
2 The versatile synthetic utility of both the allylic acetate and enal products accessible through thi
3 is a three-component coupling that joins an allylic acetate, and indole and an organo-B(pin) species
4 anol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary
7 Stille cross-coupling leads to a nonracemic allylic alcohol as a prerequisite for the introduction o
9 hydes and allenes, providing silyl-protected allylic alcohol derivatives possessing a terminal methyl
12 al beta-alkynyl carbonyl compounds employing allylic alcohol substrates in contrast to more tradition
13 productive CM coupling, the sphingosine head allylic alcohol was protected with a cyclic carbonate mo
14 are generated from the reaction of a second allylic alcohol with high selectivity in moderate to goo
16 t contain a carboxylic acid, an aldehyde, an allylic alcohol, an aryl olefin, an alpha substituent, o
17 -catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed.
19 hothiolate complex and afford trisubstituted allylic alcohols and ethers in up to 81% yield and >98%
20 of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions.
21 erived from Katsuki-Sharpless epoxidation of allylic alcohols as initiating groups for cationic cycli
22 -propanol (HFIP), polyene cyclizations using allylic alcohols as initiators gave the desired cyclized
23 lization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their p
25 Under these conditions, deoxyfluorination of allylic alcohols is effected with high chemoselectivity
27 stereochemical information contained in the allylic alcohols is transferred to the ketone products.
28 s enable the synthesis of either (Z)- or (E)-allylic alcohols regarding the order of introducing coup
29 noallylation step of amines with substituted allylic alcohols that proceeds to yield the monoallylate
30 enantioselective isomerization of secondary allylic alcohols to access ketones with a alpha-tertiary
31 ion between beta-iodoenamide derivatives and allylic alcohols to generate beta-allyloxyenamide deriva
32 A ferrocenium boronic acid salt activates allylic alcohols to generate transient carbocations that
33 olecular coupling of oxygen nucleophiles and allylic alcohols to give beta-aryloxycarbonyl compounds
34 al phosphoric acid catalyzed fluorination of allylic alcohols using aryl boronic acids as transient d
35 ctive arylative semipinacol rearrangement of allylic alcohols using diaryliodonium salts is reported.
36 Treatment of crude gamma,gamma-disubstituted allylic alcohols with NaOH, followed by acidification, a
39 antioselective bromochlorination reaction of allylic alcohols, employing readily available halogen so
40 r delta-chiral amines from readily available allylic alcohols, esters and ethers using a reductive re
41 strate classes, including 4-pentenoic acids, allylic alcohols, homoallyl amines, and bis-homoallylami
42 sformations that directly generate acyclic Z allylic alcohols, including products that contain a hind
45 ible with all classes of alcohols (benzylic, allylic, aliphatic), mediate efficient lactonization of
46 rst examples of Cu-catalyzed gamma-selective allylic alkenylation using organozinc reagents are repor
47 ications in both copper-catalyzed asymmetric allylic alkylation and copper-catalyzed asymmetric boryl
49 the indole C3 position greatly improved the allylic alkylation chemistry and enabled a highly effici
50 (DHPI) substrates in Pd-catalyzed asymmetric allylic alkylation chemistry facilitates rapid access to
51 nd highly enantioselective rhodium-catalyzed allylic alkylation of allyl benzoate with alpha-substitu
52 ymmetric palladium-catalyzed decarboxylative allylic alkylation of differentially N-protected piperaz
54 A highly enantioselective rhodium-catalyzed allylic alkylation of prochiral alpha,alpha-disubstitute
55 regio- and stereospecific rhodium-catalyzed allylic alkylation of tertiary allylic carbonates with a
56 tereo-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to for
57 elective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine l
58 constant) in palladium-catalysed asymmetric allylic alkylation reactions has proved to be extremely
59 owed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effe
60 st highly enantioselective iridium-catalyzed allylic alkylation that provides access to products bear
61 ied approach featuring a key decarboxylative allylic alkylation to access a crucial and highly conges
67 highly enantioselective palladium-catalyzed allylic alkylations with benzylic nucleophiles, activate
68 that provides access to products bearing an allylic all-carbon quaternary stereogenic center has bee
69 these have been used for the preparation of allylic amide derived 2H-chromenes using an Overman rear
73 s undergo alternative oxidative amination or allylic amination pathways, and these reactions will als
76 diates and enable the divergent synthesis of allylic amine and enamine derivatives, which are of sign
77 cal strategy for the synthesis of high-value allylic amine building blocks that does not require the
79 ed to rationalize the stereocontrol in these allylic amine formation reactions, and evidence is provi
81 - and ruthenium-free approaches to protected allylic amines and alkyl nitriles under photoredox condi
83 ctive synthesis of tri- and tetrasubstituted allylic amines based on Pd-catalyzed conversion of allyl
86 , which undergoes hydroamination to generate allylic amines instead of the enamine or imine products
90 phos ligand, hydroamination generates chiral allylic amines with high regio- and enantioselectivity.
91 observed in recent years in the synthesis of allylic amines, which are important building blocks in s
92 sses are effective toward the preparation of allylic amines, with limited potential to introduce thre
95 reveal that the cyclization, followed by 1,3-allylic amino dehydroxylation, is preceded by urea forma
96 precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosph
98 e report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting
100 intermediate, and differential activation of allylic and homoallylic alcohols in the analogues, follo
104 saghi protocol, stereoselective reduction of allylic and propargylic ketones using Noyori's catalyst,
105 enes and radical substitution reactions with allylic and vinylic bromides and chlorides were examined
109 ld, amide-directed fluorination of benzylic, allylic, and unactivated C-H bonds mediated by iron.
111 Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results
112 contemplated as allyl electrophile donor for allylic arylation via pi-allyl palladium intermediate us
115 pha C-H bonds in alcohols in the presence of allylic, benzylic, alpha-C=O, and alpha-ether C-H bonds.
117 copper catalyst, these reagents reacted with allylic bromides derived from Morita-Baylis-Hillman alco
118 selective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosph
119 ymmetric alkylation of anthrones with cyclic allylic bromides using quinidine- or quinine-derived cat
120 iously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled alph
121 d N-sulfonamides undergo a Rh(III)-catalyzed allylic C(sp(3))-H activation followed by insertion with
122 a sodium amide has been exploited for formal allylic C(sp(3))-H bond activation of alkenes under mild
123 al Pd-catalyzed aerobic oxidation reactions: allylic C-H acetoxylation of terminal alkenes and intram
124 site-selective second arylation by directed allylic C-H activation giving stereoselectively anti-gam
128 tocols for direct oxidation and amination of allylic C-H bonds (that is, C-H bonds where an adjacent
130 ger amide N-H bond in the presence of weaker allylic C-H bonds, a selectivity that is uncommon in con
131 ailable materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabl
132 ve enyne cyclization and a late-stage double allylic C-H oxidation as well as adapted Luche reduction
133 been accomplished by palladium(II)-catalyzed allylic C-H oxidation from terminal olefin precursors.
134 ployed to effect a chemo- and regioselective allylic C-H oxidation in the presence of four oxidizable
136 ore recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streaml
137 ave been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with
138 generated from the oxidative addition of the allylic carbonate, likely activates the enol silanes to
141 ion of substituted spiroketals from racemic, allylic carbonates is reported, which enables the instal
142 ium-catalyzed allylic alkylation of tertiary allylic carbonates with alkenyl cyanohydrin pronucleophi
143 he reaction between propargylic alcohols and allylic carbonates, engaging vanadium and palladium cata
144 that increasing the number of deuterated bis-allylic carbons to include both C10 and C13 leads to a m
146 reactions of nonsilylated allenes involve an allylic cation intermediate by forming a C-O bond, at th
149 onors and each proceed via cationic species: allylic cations and oxocarbenium ions, respectively.
150 palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered alpha-quater
154 An iron-catalyzed cyclization of hydroxy allylic derivatives into tetrahydropyrans possessing an
157 talyze consecutive condensation reactions of allylic diphosphate acceptor with isopentenyl diphosphat
158 hesized by joining fragments for IPP and the allylic diphosphates with a C-C bond between the methyl
161 anes from cycloalkanones, malononitrile, and allylic electrophiles, abundantly available reagent clas
162 Through modification of the leaving group of allylic electrophiles, we found that trisubstituted ally
163 onic pi-allyl Pd intermediates, derived from allylic ester carbonates and palladium(0) catalyst, were
167 ion is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioe
171 e enantioselective construction of secondary allylic fluorides bearing alpha-linear substituents.
173 o found that gamma-, beta-, homoallylic, and allylic fluorination are all possible and predictable th
175 heteroatom stabilization of the intermediate allylic free radical two sites for oxidative product for
177 nal alkenes to be selectively converted into allylic functionalized products with high stereoselectiv
178 l that the azomethine ylide stabilized by an allylic group cycloadds to [60]fullerene in an efficient
181 of alkylzirconocene nucleophiles to racemic allylic halide electrophiles were conducted using a comb
182 ot observed, while introduction of a second, allylic heteroatom to the substrate results in diminishm
183 turation of aliphatic alcohols into valuable allylic, homoallylic, and bis-homoallylic alcohols has b
186 onates add to glycolaldehyde imine to afford allylic hydroxyl allenes, and allyl boronates add to alk
189 complex, which undergoes imine addition with allylic inversion through a closed transition structure.
190 nce of a chiral copper catalyst, substituted allylic iodides couple with alpha-diazoesters to generat
191 of a 2,2'-dipyridyl ligand, diazoesters and allylic iodides react via a [2,3]-rearrangement pathway.
192 ze the addition of the hydrocarbon moiety of allylic isoprenoid diphosphates to the carbon-carbon dou
195 imidazole, and pyrazole nucleophiles via an allylic linker under neutral conditions is disclosed.
196 ienic systems and of the stereocenter at C2 (allylic methine, alpha to the carboxy group) and the pro
197 ions that are able to directly functionalize allylic methyl, methylene and methine carbons in a catal
198 etric synthesis of alpha,alpha-disubstituted allylic N-arylamines based on a palladium-catalyzed ally
199 ows for the construction of optically active allylic nitriles and dithiolanes as well as branched alp
201 Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to
204 oselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a
207 The successful strategy relied on late-stage allylic oxidations at two separate positions of the mole
210 divergent addition of substituted phenols to allylic oxides has been demonstrated using C2-symmetric
211 - and 1,4-addition of substituted phenols to allylic oxides is achieved by intercepting palladium pi-
213 lar hydroallylation of vinylarenes employing allylic phosphate electrophiles has been achieved throug
214 ve cyclizations of substrates containing a Z-allylic phosphate tethered to an alkyne are described.
216 ryl-substituted disubstituted alkenes within allylic phosphates and those with an alkyl or a silyl gr
217 electrophiles, we found that trisubstituted allylic phosphates are suitable electrophiles for asymme
218 developed reaction conditions where racemic allylic phosphates are suitable substrates using new pho
221 l-, alkenyl-, alkynyl- and alkyl-substituted allylic phosphates may thus be converted to the correspo
222 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
228 m-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford th
229 ific, nickel-catalyzed Miyaura borylation of allylic pivalates, which delivers highly enantioenriched
230 er multiple bonds with a functional group in allylic position and some examples of successful transfo
231 n liquid ammonia, MCPs bearing a C-O bond at allylic position undergo both a reductive cleavage of th
232 lyunsaturated fatty acids (PUFAs) at the bis-allylic position; indeed, pretreating cells with PUFAs c
233 enium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an
235 resonances associated with the olefinic and allylic protons as a result of them residing inside the
236 report, we describe the generation of remote allylic quaternary stereocenters beta, gamma, and delta
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
245 ueezing out the ligand from the conventional allylic S1 binding site, with proton abstraction being a
247 r dienes containing both alkene pi-bonds and allylic sigma-bonds, and the ene yields are higher with
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
253 diphosphate synthase (UPPS), and contains an allylic site (S1) in which DMAPP ionizes and a second si
254 unsaturated fatty acids (PUFAs) at their bis-allylic sites has been identified as a unique approach i
256 cemic allylboronate reagent that contains an allylic stereogenic center, additions were exceptionally
257 d reduction of the hydrazone with an in situ allylic strain controlled retro-ene reaction of an allyl
259 er BF3.OEt2 catalysis or using alcohols with allylic substituents provides exclusively the correspond
260 l pincer carbodicarbene ligand that delivers allylic substituted arenes in up to 95% yield and up to
261 different NHC-Cu-catalyzed enantioselective allylic substitution (EAS) reactions further highlights
262 of the latter resulted in mono-arylation by allylic substitution and subsequent site-selective secon
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)
270 rticular, a one-pot tandem alkyne silylation/allylic substitution sequence, in which both steps are c
272 ynthetic sequence involving enantioselective allylic substitution, cross-metathesis, dihydroxylation,
273 kinetically competent to be intermediates in allylic substitutions of branched, racemic allylic alcoh
274 are diastereoselective and enantioselective allylic substitutions with acyclic alpha-alkoxy ketones
276 become widely established, the engagement of allylic substrates in C-C bond forming reactions has thu
278 on, but prior cross couplings are limited to allylic substrates or deliver little to no enantiomeric
280 ropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally sh
281 ollowed by stereoselective preparation of an allylic sulfide by reaction of vinylzinc bromide with an
282 ery facilitates an ene-cycloisomerization of allylic-sulfide-containing alkenylidenecyclopropanes (AC
283 sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle-Kirmse reacti
284 r selectivity is obtained with both E- and Z-allylic sulfides and the reaction is also feasible with
287 venient Suzuki-Miyaura coupling of borylated allylic sulfones with various electrophiles in both inte
289 bond formation of an amide-tethered benzylic/allylic system using DDQ under neutral conditions which
291 , the direct arylation of non-functionalized allylic systems would enable access to a series of known
292 enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, ger
298 oselective fluorination of racemic, branched allylic trichloroacetimidates with Et3N.3HF is a mild an
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