cas 13002-65-8, 2-[4-[(E)-1,2-diphenylbut-1-enyl]phenoxy]-N,N-dimethyl-ethanamine

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Rh-Catalyzed Coupling of Aldehydes with Allylboronates Enables Facile Access to Ketones
We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain-walking process were involved.
Zhang, Kezhuo,Huang, Jiaxin,Zhao, Wanxiang
supporting information

(2022/02/21)

Stereoconvergent and -divergent synthesis of tetrasubstituted alkenes by nickel-catalyzed cross-couplings
We report the development of a method to diastereoselectively access tetrasubstituted alkenes via nickel-catalyzed Suzuki-Miyaura cross-couplings of enol tosylates and boronic acid esters. Either diastereomeric product was selectively accessed from a mixture of enol tosylate starting material diastereomers in a convergent reaction by judicious choice of the ligand and reaction conditions. A similar protocol also enabled a divergent synthesis of each product isomer from diastereomerically pure enol tosylates. Notably, high-throughput optimization of the monophosphine ligands was guided by chemical space analysis of the kraken library to ensure a diverse selection of ligands was examined. Stereoelectronic analysis of the results provided insight into the requirements for reactive and selective ligands in this transformation. The synthetic utility of the optimized catalytic system was then probed in the stereoselective synthesis of various tetrasubstituted alkenes, with yields up to 94% and diastereomeric ratios up to 99:1 Z/E and 93:7 E/Z observed. Moreover, a detailed computational analysis and experimental mechanistic studies provided key insights into the nature of the underlying isomerization process impacting selectivity in the cross-coupling.
Zell, Daniel,Kingston, Cian,Jermaks, Janis,Smith, Sleight R.,Seeger, Natalie,Wassmer, Jana,Sirois, Lauren E.,Han, Chong,Zhang, Haiming,Sigman, Matthew S.,Gosselin, Francis
p. 19078 - 19090
(2021/11/22)

Pd-catalyzed cross-coupling of highly sterically congested enol carbamates with grignard reagents via c-o bond activation
The palladium-catalyzed cross-coupling reaction of enol carbamates to construct highly sterically congested alkenyl compounds is presented for the first time. This protocol demonstrates the potential of using thermally stable and highly atom-economic enol electrophiles as building blocks in bulky alkene synthesis. This reaction accommodates a broad substrate scope with excellent Z/E isomer ratios, which also provides a new synthetic pathway for accessing Tamoxifen.
Chen, Zicong,So, Chau Ming
p. 3879 - 3883
(2020/06/08)

Iterative synthesis of alkenes by insertion of lithiated epoxides into boronic esters
The insertion of lithiated epoxides into boronic esters followed by thermal syn-elimination provides a stereospecific entry to alkenes. This process avoids transition metals and is amenable to iteration to provide higher substitution patterns.
Bojaryn, Kevin,Fritsch, Stefan,Hirschhaüser, Christoph
supporting information
p. 2218 - 2222
(2019/04/10)

An atom efficient synthesis of tamoxifen
The direct carbolithiation of diphenylacetylenes and their cross-coupling procedure taking advantage of the intermediate alkenyllithium reagents are presented. By employing our recently discovered highly active palladium nanoparticle based catalyst, we were able to couple an alkenyllithium reagent with a high (Z/E) selectivity (10:1) and good yield to give the breast cancer drug tamoxifen in just 2 steps from commercially available starting materials and with excellent atom economy and reaction mass efficiency.
Heijnen, Dorus,Van Zuijlen, Milan,Tosi, Filippo,Feringa, Ben L.
supporting information
p. 2315 - 2320
(2019/03/06)

Divergent Synthetic Access to E- and Z-Stereodefined All-Carbon-Substituted Olefin Scaffolds: Application to Parallel Synthesis of (E)- and (Z)-Tamoxifens
A highly substrate-general synthesis of all-carbon-substituted E- and Z-stereodefined olefins is performed. The method comprises two sets of parallel and stereocomplementary preparations of (E)- and (Z)-α,β-unsaturated esters involving two robust and distinctive reactions: 1) stereocomplementary enol tosylations using readily available TsCl/diamine/(LiCl) base reagents, and 2) stereoretentive Negishi cross-coupling using the catalysts [Pd(dppe)Cl2] (for E) and [Pd(dppb)Cl2] (for Z). The present parallel approach is categorized as both type I (convergent approach: 16 examples, 56–87 % yield) and type II (divergent approach: 18 examples, 70–95 % yield). The obtained (E)- and (Z)-α,β-unsaturated ester scaffolds are successfully transformed into various E- and Z-stereodefined known and novel olefins (8×2 derivatization arrays). As a demonstration, application to the parallel synthesis of both (E)- and (Z)-tamoxifens, a representative motif of all-carbon-substituted olefins, is accomplished in a total of eight steps with an overall yield of 58 % (average 93 %) and 57 % (average 93 %), respectively.
Ashida, Yuichiro,Honda, Atsushi,Sato, Yuka,Nakatsuji, Hidefumi,Tanabe, Yoo
p. 73 - 89
(2017/02/10)

Photoredox-Catalyzed C-H Arylation of Internal Alkenes to Tetrasubstituted Alkenes: Synthesis of Tamoxifen
Visible-light-induced direct C-H arylation of S,S-functionalized internal alkenes, that is, α-oxo ketene dithioacetals and analogues, has been efficiently realized with aryldiazonium salts (ArN2BF4) as coupling partners and Ru(bpy)s
Wang, Quannan,Yang, Xiaoge,Wu, Ping,Yu, Zhengkun
supporting information
p. 6248 - 6251
(2017/11/24)

Photochemical Activation of Tertiary Amines for Applications in Studying Cell Physiology
Representative tertiary amines were linked to the 8-cyano-7-hydroxyquinolinyl (CyHQ) photoremovable protecting group (PPG) to create photoactivatable forms suitable for use in studying cell physiology. The photoactivation of tamoxifen and 4-hydroxytamoxifen, which can be used to activate Cre recombinase and CRISPR-Cas9 gene editing, demonstrated that highly efficient release of bioactive molecules could be achieved through one- and two-photon excitation (1PE and 2PE). CyHQ-protected anilines underwent a photoaza-Claisen rearrangement instead of releasing amines. Time-resolved spectroscopic studies revealed that photorelease of the tertiary amines was extremely fast, occurring from a singlet excited state of CyHQ on the 70 ps time scale.
Asad, Naeem,Deodato, Davide,Lan, Xin,Widegren, Magnus B.,Phillips, David Lee,Du, Lili,Dore, Timothy M.
supporting information
p. 12591 - 12600
(2017/09/23)

Nickel-catalyzed three-component domino reactions of aryl grignard reagents, alkynes, and aryl halides producing tetrasubstituted alkenes
Three-component reaction of aryl Grignard reagents, alkynes, and aryl halides in the presence of 1 mol % of NiCl2 proceeded sequentially through carbomagnesiation of the alkyne followed by cross-coupling of the resulting alkenyl Grignard reagent with aryl halide to give tetrasubstituted alkenes in high yields.
Xue, Fei,Zhao, Jin,Hor, T. S. Andy,Hayashi, Tamio
supporting information
p. 3189 - 3192
(2015/03/30)

Transition-Metal-Free α-Arylation of Enolizable Aryl Ketones and Mechanistic Evidence for a Radical Process
The α-arylation of enolizable aryl ketones can be carried out with aryl halides under transition-metal-free conditions using KOtBu in DMF. The α-aryl ketones thus obtained can be used for step- and cost-economic syntheses of fused heterocycles and Tamoxifen. Mechanistic studies demonstrate the synergetic role of base and solvent for the initiation of the radical process.
Pichette Drapeau, Martin,Fabre, Indira,Grimaud, Laurence,Ciofini, Ilaria,Ollevier, Thierry,Taillefer, Marc
p. 10587 - 10591
(2015/09/02)

Efficient synthesis of polysubstituted olefins using stable palladium nanocatalyst: Applications in synthesis of tamoxifen and isocombretastatin A4
A phosphine-free stable palladium nanocatalyst was used for an efficient synthesis of polysubstituted olefins from N-tosylhydrazones and aryl iodides. This methodology was successfully utilized in the synthesis of biologically important tamoxifen and isocombretastatin A4. The nanocatalyst was easily recovered and reused without any apparent loss in size and catalytic activity.
Ganapathy, Dhandapani,Sekar, Govindasamy
supporting information
p. 3856 - 3859
(2014/08/18)

Iridium-catalyzed diborylation of benzylic C-H bonds directed by a hydrosilyl group: Synthesis of 1,1-benzyldiboronate esters
We describe a regioselective diborylation of primary benzylic C-H bonds catalyzed by [Ir(COD)OMe]2 and 4,4′-di-tert-butyl-2,2′- bipyridine (dtbpy). The hydrosilyl group acts as a traceless directing group, providing access to a range of 1,1-benzyldiboronate esters in good yields. Transformations of the 1,1-benzyldiboronate ester products include chemoselective Suzuki-Miyaura cross-couplings and synthesis of tetrasubstituted alkenyl boronate esters.
Cho, Seung Hwan,Hartwig, John F.
p. 694 - 698
(2014/01/17)

Continuous flow-processing of organometallic reagents using an advanced peristaltic pumping system and the telescoped flow synthesis of (E/Z)-tamoxifen
A new enabling technology for the pumping of organometallic reagents such as n-butyllithium, Grignard reagents, and DIBAL-H is reported, which utilises a newly developed, chemically resistant, peristaltic pumping system. Several representative examples of its use in common transformations using these reagents, including metal-halogen exchange, addition, addition-elimination, conjugate addition, and partial reduction, are reported along with examples of telescoping of the anionic reaction products. This platform allows for truly continuous pumping of these highly reactive substances (and examples are demonstrated over periods of several hours) to generate multigram quantities of products. This work culminates in an approach to the telescoped synthesis of (E/Z)-tamoxifen using continuous-flow organometallic reagent-mediated transformations.
Murray, Philip R. D.,Browne, Duncan L.,Pastre, Julio C.,Butters, Chris,Guthrie, Duncan,Ley, Steven V.
p. 1192 - 1208
(2013/10/08)

Oxidative heck arylation for the stereoselective synthesis of tetrasubstituted olefins using nitroxides as oxidants
One, two, and three! Nitroxides and dioxygen serve as oxidants in highly stereoselective oxidative Pd-catalyzed Heck arylations in which aryl boronic acids are used to synthesize triarylalkyl-substituted olefins. The reactions occur under very mild conditions at room temperature. As an example, the threefold sequential arylation of methyl acrylate is the crucial step in the stereoselective synthesis of Z-Tamoxifen.
He, Zhiheng,Kirchberg, Sylvia,Froehlich, Roland,Studer, Armido
supporting information; experimental part
p. 3699 - 3702
(2012/05/20)

Stereoselective synthesis of (E)-(trisubstituted alkenyl)borinic esters: Stereochemistry reversed by ligand in the palladium-catalyzed reaction of alkynylborates with aryl halides
"Chemical Equation Presented" The palladium-catalyzed reaction of alkynylborates with aryl halides stereoselectively gave (E)-(trisubstituted alkenyl)-9-BBNs, in which two different aryl groups were installed trans to each other.
Ishida, Naoki,Shimamoto, Yasuhiro,Murakami, Masahiro
supporting information; experimental part
p. 5434 - 5437
(2010/02/28)

Trans-stilbene as a starting material for the synthesis of tamoxifen based on palladium-catalyzed cross-coupling reactions
(Z)-Tamoxifen was synthesized from a simple olefin (trans-stilbene) in 5 steps and 40% overall yield (Z/E = 74:26). The phenyl substituted group (4-Me2NCH2CH2OC6H4) was attached by a bromination-dehydrobromination-Suzuki reaction sequence. Subsequently, the ethyl group was attached to the triarylated olefin by a bromination-Negishi reaction sequence. Both the Suzuki and Negishi cross-coupling processes are stereospecific, and the stereo-selectivity depends only on the bromination-dehydrobromination reactions. (Z)-Tamoxifen was also obtained from trans-stilbene in only 3 steps by using Heck reaction-bromination- Negishi reaction sequence in 57% overall yield (Z/E = 65:35). Georg Thieme Verlag Stuttgart.
Nunes, Carolina M.,Limberger, Jones,Poersch, Silvia,Seferin, Marcus,Monteiro, Adriano L.
experimental part
p. 2761 - 2765
(2010/01/21)

An expeditious synthesis of tamoxifen, a representative SERM (selective estrogen receptor modulator), via the three-component coupling reaction among aromatic aldehyde, cinnamyltrimethylsilane, and β-chlorophenetole
Two new synthetic pathways to the anti-cancer agent tamoxifen and its derivatives were developed. The first route involved the aldol reaction of benzyl phenyl ketone with acetaldehyde followed by Friedel-Crafts substitution with anisole in the presence of Cl2Si(OTf)2 to produce 1,1,2-triaryl-3-acetoxybutane, a precursor of the tamoxifen derivatives. The second one utilized the novel three-component coupling reaction among aromatic aldehydes, cinnamyltrimethylsilane, and aromatic nucleophiles using HfCl4 as a Lewis acid catalyst to produce 3,4,4-triarylbutene, that is also a valuable intermediate of the tamoxifen derivatives. The former strategy requires a total of 10 steps from the aldol formation to the final conversion to tamoxifen, whereas the latter needs only three or four steps to produce tamoxifen and droloxifene including the installation of the side-chain moiety and the base-induced double-bond migration to form the tetra-substituted olefin structure. This synthetic strategy seems to serve as a new and practical pathway to prepare not only the tamoxifen derivatives but also the other SERMs (selective estrogen receptor modulators) including estrogen-dependent breast cancer and osteoporosis agents.
Shiina, Isamu,Sano, Yoshiyuki,Nakata, Kenya,Suzuki, Masahiko,Yokoyama, Toshikazu,Sasaki, Akane,Orikasa, Tomoko,Miyamoto, Tomomi,Ikekita, Masahiko,Nagahara, Yukitoshi,Hasome, Yoshimune
p. 7599 - 7617
(2008/03/14)

Carbolithiation of diphenylacetylene as a stereoselective route to (Z)-tamoxifen and related tetrasubstituted olefins
(Chemical Equation Presented) Carbolithiation of diphenylacetylene can be exploited to generate (E)-1-lithio-1,2-diphenylalkyl-1-enes which can be reacted in situ with triisopropylborate to stereoselectively provide (E)-1,2-diphenyl-1-alkylene boronic acids. These tetrasubstituted vinylboronic acids served as versatile intermediates for the generation of tetrasubstituted olefins with retention of stereochemistry. The application of this method for the stereoselective synthesis of (Z)-tamoxifen and related analogues is described.
McKinley, Neola F.,O'Shea, Donal F.
p. 9552 - 9555
(2007/10/03)

Facile synthesis of multisubstituted buta-1,3-dienes via Suzuki-Miyaura and Kumada cross-coupling strategy of 2,4-diiodo-buta-1-enes with arylboronic acids and Grignard reagents
One-pot Suzuki-Miyaura-type and Kumada-type cross-coupling reactions of 2,4-diiodo-buta-l-enes with arylboronic acids and alkyl/aryl magnesium bromides were carried out in the presence of accessibly simple catalysts under mild conditions. As a result, some 1,1,2-trisubstituted buta-1,3-dienes were obtained including the Tamoxifen-type, which have potential adjuvant therapy in women who have suffered from breast cancer and cyclooxygenase-2-type (COX-2-type) inhibitors, some of which have been proved to elicit efficient anti-inflammatory analgesic activities and less adverse gastrointestinal side effects and to be very useful in the prophylactic treatment of a wide variety of cancers and neurodegenerative disorders. The Royal Society of Chemistry 2005.
Shao, Li-Xiong,Shi, Min
p. 1828 - 1831
(2007/10/03)

Stereoselective cross-coupling reaction of 1,1-diboryl-1-alkenes with electrophiles: A highly stereocontrolled approach to 1,1,2-triaryl-1-alkenes
Palladium-catalyzed cross-coupling reaction of 1,1-diboryl-1-alkenes with aryl and alkenyl iodides was found to proceed stereoselectively, giving rise to the corresponding mono-coupled product as a single diastereomer with E-configuration. Second coupling of the initial product with another aryl iodide affords diverse triarylalkenes in their stereochemically pure form. This highly stereoselective approach for triarylalkenes allows one to synthesize both diastereomers in one pot from 1,1-diboryl-1-alkenes. Copyright
Shimizu, Masaki,Nakamaki, Chihiro,Shimono, Katsuhiro,Schelper, Michael,Kurahashi, Takuya,Hiyama, Tamejiro
p. 12506 - 12507
(2007/10/03)

Wittig-Horner approach for the synthesis of tamoxifen
A stereoselective synthesis of Z-tamoxifen, a tetra-substituted alkene with antiestrogenic activity, is described. The Wittig-Horner reaction has been employed as the key step to establish the olefin stereochemistry. Copyright Taylor & Francis, Inc.
Pandey, Rajesh K.,Wakharkar,Kumar, Pradeep
p. 2795 - 2800
(2007/10/03)

Catalytic carbometalation/cross-coupling sequence across alkynyl(2-pyridyl)silanes leading to a diversity-oriented synthesis of tamoxifen-type tetrasubstituted olefins
A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereo-controlled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the order use of the aryl iodides in the sequence.
Kamei, Toshiyuki,Itami, Kenichiro,Yoshida, Jun-Ichi
p. 1824 - 1835
(2007/10/03)

Short-step synthesis of tamoxifen and its derivatives via the three-component coupling reaction and migration of the double bond
The anti-tumor agent, tamoxifen, is easily synthesized by the successive allylation of benzaldehyde and the Friedel-Crafts alkylation reaction of anisole with the intermediary homoallyl silyl ethers, followed by the migration of the double bond to form the desired tetra-substituted ethylenes. Several derivatives of tamoxifen are also produced according to a similar synthetic strategy.
Shiina, Isamu,Suzuki, Masahiko,Yokoyama, Kazutoshi
p. 965 - 967
(2007/10/03)

Diversity-Oriented Synthesis of Tamoxifen-type Tetrasubstituted Olefins
A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereocontrolled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the applying order of aryl iodides into the sequence. Copyright
Itami, Kenichiro,Kamei, Toshiyuki,Yoshida, Jun-Ichi
p. 14670 - 14671
(2007/10/03)

Parallel synthesis of tamoxifen and derivatives on solid support via resin capture
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Brown, S. David,Armstrong, Robert W.
p. 7076 - 7077
(2007/10/03)

Stereoselective Olefin Formation from the Dehydration of 1-(p-Alkoxyphenyl)-1,2-diphenylbutan-1-ols: Application to the Synthesis of Tamoxifen
Acid-catalysed dehydration of either diastereoisomer of a 1-(p-alkoxyphenyl)-1,2-diphenylbutan-1-ol gives mainly the Z isomer of the but-1-ene via a common carbenium ion intermediate that can be regenerated by protonation of the (Z)- or (E)-butene with fluorosulphonic acid.Highly stereoselective syn eliminations were achieved by treatment of the butan-1-ols with base and carbon disulphide but dehydrations using N,N,N-triethylammonio-N'-methoxycarbonylsulphamidate proceeded mainly via a carbenium ion.Aspects of the stereoselectivity of the reactions are discussed.The methods can be applied to give simple stereoselective syntheses of the anti-cancer drug tamoxifen.
McCague, Raymond
p. 1011 - 1016
(2007/10/02)

Synthesis of cis- and trans-tamoxifen
The synthesis of cis-tamoxifen, non antiestrogenic tetrasubstituted olefin, was achieved via carboalumination of diphenylacetylene as a key step.Conversion to the antiestrogenic trans-tamoxifen was achieved by facile cis-trans isomerization of the corresponding phenol by acid or catalysts.
Al-Hassan, Mohammed I.
p. 1247 - 1252
(2007/10/02)

A single-step synthesis of tamoxifen using palladium-catalyzed cross-coupling
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Al-Hassan
p. 816 - 817
(2007/10/02)

The use of Octafluorotoluene and Pentafluoropyridine in the Synthesis of Pure Z and E Isomers of Derivatives of Tamoxifen -1-butene>
Octafluorotoluene and pentafluoropyridine have been used in the synthesis of pure Z and E isomers of derivatives of the anticancer drug, tamoxifen (1).The isomeric ethers derived by reaction of these perfluoroarenes with an E/Z mixture of 1,2-diphenyl-1-(4-hydroxyphenyl)-1-butene (3) and (4) were easily separated.A process is described for conversion of the E/Z mixtures into one isomer.Cleavage of the ethers regenerated the phenol (3) or (4) of pure stereochemical configuration and the Z-isomer (3) was used for the synthesis of tamoxifen (1) and various monomeric and dimeric analogues.Other perfluoroarenes were less useful.A short synthesis involving early introduction of the perfluorotolyl group is also described.
Jarman, Michael,McCague, Raymond
p. 1342 - 1388
(2007/10/02)