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Synthesis of allylic amines


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Tsuji-Trost Reaction

Recent Literature

A dehydrative allylation of allyl alcohol with amines provides various allyl amines in the presence of MoO3/TiO2 as solid catalyst. The catalyst can be reused three times without loss of activity.
Y. Kon, T. Nakashima, T. Fujitani, T. Murayama, W. Ueda, Synlett, 2019, 30, 287-292.

A phosphine-borane compound is an effective ligand for palladium-catalyzed direct allylic amination of allylic alcohols with secondary amines in short reaction times at room temperature.
G. Hirata, H. Satomura, H. Kumagae, A. Shimizu, G. Onodera, M. Kimura, Org. Lett., 2017, 19, 6148-6151.

The use of aqueous ammonia is essential for a palladium-catalyzed allylic amination for the preparation of primary amines. It is noteworthy that ammonia gas did not react at all. The first catalytic asymmetric synthesis using aqueous ammonia as a nitrogen source has also been demonstrated.
T. Nagano, S. Kobayashi, J. Am. Chem. Soc., 2008, 131, 4200-4201.

Phosphinoamide-scaffolded heterobimetallic palladium-titanium complexes are highly effective catalysts for allylic aminations of allylic chlorides with hindered secondary amine nucleophiles. Various sterically bulky secondary amines are efficiently allylated in high yields with low catalyst loadings. Piperidine and pyrrolidine products are also efficiently generated via intramolecular aminations.
W. K. Walker, D. L. Anderson, R. W. Stokes, S. J. Smith, D. J. Michaelis, Org. Lett., 2015, 17, 752-755.

A Facile Highly Regio- and Stereoselective Preparation of N-Tosyl Allylic Amines from Allylic Alcohols and Tosyl Isocyanate via Palladium(II)-Catalyzed Aminopalladation-β-Heteroatom Elimination
A. Lei, X. Lu, Org. Lett., 2000, 2, 2357-2360.

An iridium-catalyzed allylic amination of branched and linear allylic carbonates provides branched amines in high selectivity. The use of a polar solvent such as EtOH is essential for obtaining products in high yield. Both secondary and primary amines could be used for this reaction. When a primary amine was used, selective monoallylation occurred.
R. Takeuchi, N. Ue, K. Tanabe, K. Yamashita, N. Shiga, J. Am. Chem. Soc., 2001, 123, 9525-9534.

The reactivity of thianthrene-based nitrogen sources enables allylic amination of alkenes to directly afford alkyl allylamines. Iminothianthrenes can be prepared from primary amines in a single step.
Q. Cheng, J. Chen, S. Lin, T. Ritter, J. Am. Chem. Soc., 2020, 142, 17287-17293.

The combination of a palladium catalyst, a bidentate phosphine ligand, and duroquinone enables a catalytic intermolecular oxidative amination of unactivated olefins with primary aliphatic amines provides a range of secondary allylic amines in good yields with excellent regio- and stereoselectivity. The reaction proceeds by allylic C(sp3)-H activation and nucleophilic amination.
M. Li, Y. Jin, Y. Chen, W. Wu, H. Jiang, J. Am. Chem. Soc., 2023, 145, 9448-9453.

An iridium complex catalyzes pH-dependent selective N-allylation or N-alkylation of amines with allylic alcohols in outstanding yields with water as the environmental benign solvent.
N. Luo, Y. Zhong, H. Shui, R. Luo, J. Org. Chem., 2021, 86, 15509-15521.

A visible light-induced palladium-catalyzed homologative three-component synthesis of a broad range of allylic amines involves two distinct cycles enabled by the same Pd(0) catalyst: a visible light-induced hybrid radical alkyl Heck reaction between 1,1-dielectrophile and styrene, followed by the "in dark" classical Tsuji-Trost-type allylic substitution reaction.
N. Kvasovs, J. Fang, F. Kliuev, V. Gevorgyan, J. Am. Chem. Soc., 2023, 145, 18497-18505.

The combination of Pd(OAc)2/P(OPh)3 catalyzed Tsuji-Trost-type allylic aminations under aerobic conditions at very low catalyst loadings. Both aromatic and aliphatic secondary amines were transformed into the corresponding allylic amines in the presence of allylic phosphates as electrophiles. Other electrophiles, such as allylic acetate and carbonate, were marginally reactive.
T. Yurino, S. Saito, M. Ichihashi, T. Ohkuma, J. Org. Chem., 2022, 87, 2864-2872.

The combination of Mg2+ and PF6- as counteranion catalyzes a transition-metal-free dehydrative cross-coupling of unactivated primary/secondary alcohols with amines/amides under environmentally benign conditions. A wide range of allylic alcohols and amines/amides were tolerated well in this efficient transformation.
H. Xing, M. Chen, D. Zhang, Z. Geng, P. Xie, T.-P. Loh, Org. Lett., 2022, 24, 5657-5662.

A planar chiral indenyl rhodium complex for enantioselective C-H functionalization catalysis is capable of catalyzing an asymmetric allylic C-H amidation of unactivated olefins, delivering a wide range of high-value enantioenriched allylic amide products in good yields with excellent regio- and enantioselectivity.
C. M. B. Farr, A. M. Kazerouni, B. Park, C. D. Poff, J. Won, K. R. Sharp, M.-H. Baik, S. B. Blakey, J. Am. Chem. Soc., 2020, 142, 13996-14004.

Ir(III) catalysis enables an efficient intermolecular branch-selective allylic C-H amidation in good yields and regioselectivities. The reaction proceeds through initial allylic C-H activation followed by a subsequent oxidative amidation with readily available dioxazolones as nitrenoid precursors.
H. Lei, T. Rovis, J. Am. Chem. Soc., 2019, 141, 2268-2273.

A metal-free allylic amination of alkenes with simple sulfonamides and sulfamates allows the introduction of a wide range of nitrogen functionality at the allylic position of alkenes with unique regioselectivity and no allylic transposition in the presence of phosphine selenides or selenoureas as catalysts.
W. P. Teh, D. C. Obenschain, B. M. Black, F. E. Michael, J. Am. Chem. Soc., 2020, 142, 16716-16722.

The Z geometry of methyl (Z)-3-monosubstituted-2-alkenyl carbonate was completely retained in iridium complex-catalyzed allylic amination. Various (Z)-allylic amines were obtained in high selectivity by allylic amination of methyl (Z)-3-monosubstituted-2-alkenyl carbonate.
R. Takeuchi, N. Shiga, Org. Lett., 1999, 1, 265-267.

Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N-Boc ethyl oxamate to deliver the corresponding N-Boc allylic amines. Subsequent N-methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts.
B. C. van Veen, S. M. Wales, J. Clayden, J. Org. Chem., 2021, 86, 8538-8543.

A cobalt-catalyzed allylation of amides with styrenes, in which DMSO was used as both the solvent and the α-methylene source, provides privileged allylic amines in high yields, and selectivity for the (E)-isomer of the linear product.
X. Zhang, Z. Zhou, H. Xu, X. Xu, X. Yu, W. Yi, Org. Lett., 2019, 21, 7248-7253.

A simple Re2O7-catalyzed direct dehydrative coupling between π-activated alcohols with electron-deficient amines has been achieved under mild and open flask conditions. The protocol alows the conversion of allylic, benzylic, and propargylic alcohols. The mechanistic proof for the SN1-type process has also been provided.
B. G. Das, R. Nallagonda, P. Ghorai, J. Org. Chem., 2012, 77, 5577-5583.

A robust and convenient molybdenum-catalyzed regioselective allylic amination of tertiary allylic carbonates provides α,α-disubstituted allylic amines in high yield with complete regioselectivity in ethanol as green solvent. Both aromatic and aliphatic amines react with various tertiary allylic alcohol derivatives. The catalyst can be recycled through simple centrifugation techniques.
S. Khan, M. Salman, Y. Wang, J. Zhang, A. Khan, J. Org. Chem., 2023, 88, 11992-11999.

Iridium catalysts derived from a phosphoramidite containing a biphenolate group, one distal chiral substituent at nitrogen and a large achiral cycloalkyl group were shown to react in all cases examined with nearly the same rates, regioselectivities, and enantioselectivities as catalysts derived from the previously reported, more elaborate ligands.
A. Leitner, S. Shekhar, M. J. Pouy, J. F. Hartwig, J. Am. Chem. Soc., 2005, 127, 15506-15514.

Palladium-catalyzed isomerization of readily accessible racemic, branched aromatic allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave branched allylic amines, ethers, and alkyls in good yield with high regioisomeric and enantiomeric selectivity.
S. Shekhar, B. Trantow, A. Leitner, J. F. Hartwig, J. Am. Chem. Soc., 2006, 128, 11770-11771.

The allylic amination and etherification of a broad range of allylic carbonates occurred in high yields and with high regioselectivities and enantioselectivities with an activated metallacyclic iridium catalyst containing a bis-naphthethylamino group.
A. Leitner, C. Shu, J. F. Hartwig, Org. Lett., 2005, 7, 1093-1096.

An iridium-catalyzed enantioselective allylic amination of (E)-cinnamyl and terminal aliphatic allylic carbonates using chiral phosphoramidites as ligands provided branched secondary and tertiary allylic amines in high yields with excellent regio- and enantioselectivity. Reactions in THF displayed the most suitable balance of rate and enantioselectivity.
T. Ohmura, J. F. Hartwig, J. Am. Chem. Soc., 2002, 124, 15164-15165.

Robust air-stable cyclometalated π-allyliridium C,O-benzoates modified by (S)-tol-BINAP catalyze an enantioselective allylic amination of racemic alkyl-substituted allylic acetates with secondary aliphatic amines with high levels of enantioselectivity and complete branched regioselectivity.
W.-O. Jung, M. Yoo, M. M. Migliozzy, J. R. Zbieg, C. E. Stivala, M. J. Krische, Org. Lett., 2022, 24, 441-445.

A cobalt-catalyzed highly branched- and enantioselective allylic amination of racemic branched allylic carbonates bearing alkyl groups with both aromatic and aliphatic amines provides allylic amines in high yields with exclusively branched selectivity and excellent enantioselectivities under mild reaction conditions.
S. Ghorai, S. S. Chirke, W.-B. Xu, J.-F. Chen, C. Li, J. Am. Chem. Soc., 2019, 141, 11430-11434.

An air- and water-stable π-allyliridium complex catalyzes highly regio- and enantioselective Tsuji-Trost-type aminations of racemic branched alkyl-substituted allylic acetates with primary or secondary (hetero)aromatic amines.
S. W. Kim, L. A. Schwartz, J. R. Zbieg, C. E. Stivala, M. J. Krische, J. Am. Chem. Soc., 2019, 141, 671-676.

Chiral bis(oxazoline)alkynylphosphine ligands can be used in Rh-catalyzed highly regio- and enantioselective allylic amination reactions of racemic 1,2-disubstituted allylic phosphates to provide chiral 1,2-disubstituted allylic amines in very good yield with >20:1 branched/linear ratio and excellent ee.
W.-B. Xu, M. Sun, M. Shu, C. Li, J. Am. Chem. Soc., 2021, 143, 8255-8260.

An efficient aerobic linear allylic C-H amination under palladium(II)/bis-sulfoxide/Brřnsted base catalysis operates under operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant.
C. P. Pattillo, I. I. Strambeanu, P. Calleja, N. A. Vermeulen, T. Mizuno, M. C. White, J. Am. Chem. Soc., 2016, 138, 1265-1272.

A direct catalytic amination of allylic alcohols without the use of activating reagents is promoted by the combination of platinum and the large bite-angle ligand DPEphos. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of various monoallylated products in good yield.
M. Utsunomiya, Y. Miyamoto, J. Ipposhi, T. Ohshima, K. Mashima, Org. Lett., 2007, 9, 3371-3374.

A ligand-free copper-catalyzed hydroamination of allenes with cyclic secondary amines or anilines derivatives provides (E)-allylamines under smooth conditions with total regio- and stereoselectivity.
R. Blieck, J. Bahri, M. Taillefer, F. Monnier, Org. Lett., 2016, 18, 1482-1485.

A rhodium-catalyzed regioselective amination of tertiary allylic trichloroacetimidates with unactivated aromatic amines is a direct and efficient approach to the preparation of α,α-disubstituted allylic aryl amines in good yield and with excellent regioselectivity. This method enables the conversion of unactivated primary and secondary amines and the preparation of reverse prenylated indoles in two steps.
J. S. Arnold, G. T. Cizio, H. M. Nguyen, Org. Lett., 2011, 13, 5576-5579.

The use of a carbodicarbene-based pincer ligand scaffold enables a site-selective Rh(I)-catalyzed intermolecular hydroamination of 1,3-dienes with aryl and alkyl amines. Transformations proceed in the presence of 1.0-5.0 mol % Rh complex at 35 - 120 °C; allylic amines are obtained in up to 97% yield and with >98:2 site selectivity.
M. J. Goldfogel, C. C. Roberts, S. J. Meek, J. Am. Chem. Soc., 2014, 136, 6227-6230.

A modular, practical, and general palladium-catalyzed, radical three-component coupling enables selective 1,4-difunctionalization of unactivated 1,3-dienes, such as butadiene, by employing different commercially available nitrogen-, oxygen-, sulfur-, or carbon-based nucleophiles and unactivated alkyl bromides.
H.-M. Huang, P. Bellotti, P. M. Pfüger, J. L. Schwarz, B. Heidrich, F. Glorius, J. Am. Chem. Soc., 2020, 142, 10173-10183.

A combination of N-bromoimide and DBU enables allylic amination reactions of alkenes, in which both internal and external nitrogen nucleophiles can be installed directly. Dual activation of NBS or NBP by DBU leads to more electrophilic bromine and more nucleophilic nitrogen atoms simultaneously. This protocol provides a complementary access to allylic amination under mild conditions.
Y. Wei, F. Liang, X. Zhang, Org. Lett., 2013, 15, 5186-5189.

A gold(I)-catalyzed decarboxylative amination of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement in H2O allows the synthesis of substituted N-tosyl allylic amines in good yield, regioselectivity, and stereoselectivity. This transformation represents an efficient and environmentally benign protocol for the synthesis of N-tosyl allylic amines.
D. Xing, D. Yang, Org. Lett., 2010, 12, 1068-1071.

An oxidative decarboxylation of β,γ-unsaturated carboxylic acids mediated by PhI(OAc)2 gives the corresponding allylic acetates. In addition, a decarboxylative C-N bond formation was achieved. Mechanistic studies suggest an unique reactivity of hypervalent iodine reagents in this ionic oxidative decarboxylation.
K. Kiyokawa, S. Yahata, T. Kojima, S. Minakata, Org. Lett., 2014, 16, 4646-4649.

A rhodium-catalyzed regioselective amination of secondary allylic trichloroacetimidates with unactivated aromatic amines gives N-arylamines in high yields and regioselectivity, favoring the branched amination products. The presence of the trichloroacetimidate leaving group was found to be critical for successful regioselective amination reactions with unactivated aromatic amines.
J. S. Arnold, R. F. Stone, H. M. Nguyen, Org. Lett., 2010, 12, 4580-4583.

Reductive amination of aldehydes and ketones with the InCl3/Et3SiH/MeOH system is highly chemoselective and can be applied to various cyclic, acyclic, aromatic, and aliphatic amines. Functionalities including ester, hydroxyl, carboxylic acid, and olefin are tolerated.
O.-Y. Lee, K.-L. Law, C.-Y. Ho, D. Yang, J. Org. Chem., 2008, 73, 8829-8837.

A direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity occurs without base in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand.
D. J. Weix, D. Marković, M. Ueda, J. F. Hartwig, Org. Lett., 2009, 11, 2944-2947.

Hydroamination of substituted allenes with benzyl carbamate catalyzed by (NHC)AuCl and AgOTf in dioxane led to isolation of allylic carbamates in good yield as single regio- and diastereomers.
R. E. Kinder, Z. Zhang, R. A. Widenhoefer, Org. Lett., 2008, 10, 3157-3159.

A protocol for the dehydrative amination of alcohols in water using a water-soluble calix[4]resorcinarene sulfonic acid as a reusable multifunctional catalyst allows an environmentally benign synthesis of benzylic and allylic amines. The aqueous phase containing the catalyst can be readily recycled.
S. Shirakawa, S. Shimizu, Synlett, 2008, 1539-1542.

KF-Celite is an efficient, inexpensive, noncorrosive, and environmentally friendly catalyst for the allylation of anilines. By using only a 1/1.2 stoichiometric ratio of electrophilic reagent to aniline, monoallylated products are obtained in high isolated yields in very short reaction times.
V. Pace, F. Martínez, M. Fernández, J. V. Sinisterra, A. R. Alcántara, Org. Lett., 2007, 9, 2661-2664.

Iridium-catalyzed allylation of potassium trifluoroacetamide or the highly reactive ammonia equivalent lithium di-tert-butyliminodicarboxylate forms a range of conveniently protected, primary, α-branched allylic amines in high yields, high branched-to-linear regioselectivities, and high enantiomeric excess.
M. J. Pouy, A. Leitner, D. J. Weix, S. Ueno, J. F. Hartwig, Org. Lett., 2007, 9, 3949-3952.

A Pd-catalysed termolecular allenylation cascade followed by a Ru catalysed RCM process affords a diverse range of Δ3-aryl/heteroaryl substituted five-seven membered nitrogen and oxygen heterocycles.
H. A. Dondas, B. Clique, B. Cetinkaya, R. Grigg, C. Kilner, J. Morris, V. Sridharan, Tetrahedron, 2005, 61, 10652-10666.

A Ni-catalyzed intermolecular enantioselective hydroamination of branched 1,3-dienes with linear or α-branched aliphatic primary amines or secondary amines provides valuable chiral allylic amines. The reaction is broadly applicable and highly regio-, chemo-, and enantioselective.
G. Tran, W. Shao, C. Mazet, J. Am. Chem. Soc., 2019, 141, 14814-14822.

Various allyl carbonates have been converted under Fe catalysis into essentially regio- and stereoisomerically pure allyl amines. Catalytic amounts of piperidinium hydrochloride as a buffer retard catalyst decomposition.
B. Plietker, Angew. Chem. Int. Ed., 2006, 45, 6053-6056.

A catalytic asymmetric synthesis of unprotected secondary allylic amines based on the aza-Claisen rearrangement of N-aryl- and N-alkyl-substituted trifluoroacetimidates has been developed, which provides the targeted products with excellent enantioselectivity.
Z.-q. Xin, D. F. Fischer, R. Peters, Synlett, 2008, 1495-1499.

COP-Cl catalyzes the rearrangement of (E)-allylic trichloroacetimidates to provide transposed allylic trichloroacetamides of high enantiopurity. This practical method for transforming prochiral allylic alcohols to enantioenriched allylic amines offers high functional group compatibility.
C. E. Anderson, L. E. Overman, J. Am. Chem. Soc., 2003, 125, 12412-12413.

Privileged allylic amine structures can be constructed in a regioselective, stereoselective, and diversity-oriented manner by a novel palladium-catalyzed four-component assembly based on allenylboronate platform. A short synthesis of rolipram is also demonstrated.
K. Tonogaki, K. Itami, J.-I. Yoshida, J. Am. Chem. Soc., 2006, 128, 1464-1465.

The synthesis and properties of different planar chiral 1-phosphino-2-sulfenylferrocene ligands are reported. Very high enantioselectivities were obtained in the palladium-catalyzed allylic substitution of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and nitrogen nucleophiles using readily available tert-butylsulfenyl derivatives.
O. G. Mancheno, J. Priego, S. Cabrera, R. G. Arrayas, T. Llamas, J. C. Carretero, J. Org. Chem., 2003, 68, 3679-3686.

A mild, gold(I)-catalyzed hydroamination of 1,3-dienes is reported. Various carbamates and sulfonamides add to conjugated dienes to affort protected allylic amines in good to high yields.
C. Brouwer, C. He, Angew. Chem. Int. Ed., 2006, 45, 1744-1747.

Bi(OTf)3/Cu(CH3CN)4PF6 efficiently catalyzes an intermolecular 1:1 hydroamination of 1,3-dienes with various carbamates, sulfonamides, and carboxamides to afford allylic amines in good yield.
H. Qin, N. Yamagiwa, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc., 2006, 128, 1611-1614.

An unprecedented regio-controllable Ir-catalyzed allylic amination of unactivated dienyl and trienyl allylic alcohols provides C1-, C3-, and C5-/C7-amination products. Key to this protocol is the use of secondary amines as the amination reagents and scandium triflate as additive.
S. Tang, Z. Li, Y. Shao, J. Sun, Org. Lett., 2019, 21, 7228-7232.

An unprecedented regio-controllable Ir-catalyzed allylic amination of unactivated dienyl and trienyl allylic alcohols provides C1-, C3-, and C5-/C7-amination products. Key to this protocol is the use of secondary amines as the amination reagents and scandium triflate as additive.
S. Tang, Z. Li, Y. Shao, J. Sun, Org. Lett., 2019, 21, 7228-7232.

A Pd-catalyzed asymmetric allylic amination of 4-substituted 2-acetoxybut-3-enoates with amines provides chiral α,β-unsaturated γ-amino esters in good yield and high ee. The products can be conveniently transformed to chiral γ-amino acid/alcohol derivatives and chiral γ-lactams.
C. Xia, J. Shen, D. Liu, W. Zhang, Org. Lett., 2017, 19, 4251-4254.

An enantioselective alkoxycarbonylation-amination cascade process of terminal allenes with CO, methanol, and arylamines proceeds under mild conditions (r.t., ambient pressure CO) via oxidative Pd(II) catalysis using a chiral aromatic spiroketal-based diphosphine ligand and a Cu(II) salt as an oxidant to afford various α-methylene-β-arylamino acid esters in good yields with excellent enantioselectivity and high regioselectivity.
J. Liu, Z. Han, X. Wang, Z. Wang, K. Ding, J. Am. Chem. Soc., 2015, 137, 15346-15349.

A direct Fe-catalyzed synthesis of β-alkyl N-aryl aza Baylis-Hillman (ABH) adducts involves the formation of a C–N bond via a nitroso-ene reaction. This is a simple, fast, and best alternate method to overcome the substrate scope limitations of the ABH reaction. Various arylhydroxylamines reacted with esters, aldehydes, ketone, and nitriles to yield the corresponding products in good yields.
S. Murru, A. A. Gallo, R. S. Srivastava, J. Org. Chem., 2012, 77, 7119-7123.

A mild and efficient photocatalytic vinylogous reaction of dienolates with N-amino pyridinium salts provides γ-amido carbonyl compounds. This process is high-yielding, scalable, and tolerates a broad range of starting materials.
K. F. Szabó, K. Goliszewska, J. Szurmak, K. Rybicka-Jasińska, D. Gryko, Org. Lett., 2022, 24, 8120-8124.

A palladium-catalyzed allylic amination enables an asymmetric synthesis of α,α-disubstituted allylic N-arylamines from highly modular vinyl cyclic carbonates and unactivated aromatic amine nucleophiles. The catalytic process features minimal waste production, high asymmetric induction, and operational simplicity.
A. Cai, W. Guo, L. Martínez-Rodríguez, A. W. Kleij, J. Am. Chem. Soc., 2016, 138, 14194-14197.

A regio- and enantioselective amination of racemic tertiary allylic trichloroacetimidates with a variety of aniline nucleophiles in the presence of a chiral diene-ligated rhodium catalyst is a direct and efficient route to chiral α,α-disubstituted allylic N-arylamines in good yields with very good levels of regio- and enantioselectivity.
J. S. Arnold, H. M. Nguyen, J. Am. Chem. Soc., 2012, 134, 8380-8383.

A highly enantioselective and catalytic vinylation of aldehydes leads to allylic alcohols that are then transformed to the allylic amines via Overman's [3,3]-sigmatropic rearrangement of imidates. Oxidative cleavage of the allylic amines furnishes amino acids in good yields and excellent ee's. The scope and utility of this method are demonstrated by the synthesis of challenging allylic amines and their subsequent transformation to valuable nonproteinogenic amino acids, including both D and L configured (1-adamantyl)glycine.
Y. K. Chen. A. E. Lurain, P. J. Walsh, J. Am. Chem. Soc., 2002, 124, 12225-12231.

3-Pyrroline has been prepared from (Z)-1,4-dichloro-2-butene in three steps in an overall yield of 74%. The Delépine Reaction permitted the monoamination of the substrate in practically quantitative yields. The subsequent ring-closing reaction was less efficient.
S. Brandänge, B. Rodriquez, Synthesis, 1988, 347-348.

The synthesis of isomerically pure allylic amines, including farnesyl amine, is achieved in excellent yields using a modified Gabriel synthesis.
S. E. Sen, S. L. Roach, Synthesis, 1995, 756-758.

Conjugated enynes undergo selective 1,4-hydroamination under Pd catalysis to deliver chiral allenes with pendant allylic amines. Several primary and secondary aliphatic and aryl-substituted amines couple with a wide range of mono- and disubstituted enynes in a nonenantioselective reaction where DPEphos serves as the ligand. Benzophenone can be used as an ammonia surrogate.
N. J. Adamson, H. Jeddi, S. J. Malcolmson, J. Am. Chem. Soc., 2019, 141, 8574-8583.

The utilization of unprotected NH2OH, which is not only an oxygen nucleophile but also a nitrogen nucleophile, in iridium-catalyzed allylic substitution provides N-(1-allyl)hydroxylamines in good to high yields with high level of chemoselectivities, regioselectivities, and enantioselectivities under mild, carefully adjusted reaction conditions.
J. Chen, Q. Liang, X. Zhao, Org. Lett., 2019, 21, 5383-5386.

A HFIP-assisted allenamide activation enables metal-free regioselective intermolecular interception of amines to provide 1,3-diamines. Exclusive N-chemoselectivity and regioselectivity were achieved for a broad range of substrates. Experimental mechanistic studies revealed that 1,1,1,3,3,3-hexafluoro-2-propanol mediates the proton transfer for activation of the allenamide.
K. Sagar, T. R. Pradhan, A. O. Farah, H. R. Wise, B. C. Merja, M. Srimannarayana, P. H.-Y. Cheong, J. K. Park, Org. Lett., 2023, 25, 5574-5578.

Intramolecular addition of tosylureas to allenes is highly syn-/anti-diastereoselective when employing a palladium or rhodium-based catalytic system and affords 1,3-cyclic ureas in excellent yields. The obtained tetrahydropyrimidinones are easily deprotected and modified.
A. G. A. Geissler, K. R. Riesterer, B. Breit, Org. Lett., 2021, 23, 9168-9172.

A boryl-directed intermolecular C-H amination of allyl N-methyliminodiacetyl boronates (B(MIDA)s) and propargylic B(MIDA)s provide α-amino boronates with an exceptionally high level of site-selectivity. A wide variety of highly functionalized secondary and tertiary α-amino boronates are formed in very good yields under mild reaction conditions.
Y. Liu, Z.-H. Chen, Y. Li, J. Qian, Q. Li, H. Wang, J. Am. Chem. Soc., 2022, 144, 14380-14387.


Catalytic access to thermodynamically less stable Z-alkenes have relied upon kinetic control of the reaction. A mild and simple orthogonal approach proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer via a photochemical pumping mechanism.
K. Singh, S. J. Staig, J. D. Weaver, J. Am. Chem. Soc., 2014, 136, 5275-5278.