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Synthesis of vinyl iodides


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A halide-exchange reaction of vinyl bromides with potassium iodide proceeds smoothly in the presence of a copper catalyst under mild reaction conditions to provide the corresponding vinyl iodides stereospecifically and in good yields.
X. Feng, H. Zhang, W. Lu, Y. Yamamoto, A. I. Almansour, N. Arumugam, R. S. Kumar, M. Bao, Synthesis, 2017, 49, 2727-2732.

A mild and general copper(I)-catalyzed conversion of aryl, heteroaryl, and vinyl bromides into the corresponding iodides was developed. Various functional groups and even N-H containing substrates such as sulfonamides, amides, and indoles are compatible with the reaction conditions.
A. Klapars, S. L. Buchwald, J. Am. Chem. Soc., 2002, 124, 14844-14845.

A highly efficient in situ generation of the Schwartz reagent provides a convenient method for the reduction of amides to aldehydes and the regioselective hydrozirconation-iodination of alkynes and alkenes. These single-step processes proceed in very short reaction time, show excellent functional group compatibility, and use inexpensive and long-storage stable reducing reagents.
Y. Zhao, V. Snieckus, Org. Lett., 2014, 16, 390-393.

A ruthenium-catalyzed regioselective hydrohalogenation reaction of alkynes provides Markovnikov products under mild conditions using simple halogen sources such as KI, ZnBr2, and ZnCl2. Alkynes derived from bioactive molecules such as l-(-)-borneol, l-menthol, and estrone were also suitable for the transformation, demonstrating the potential synthetic value of this method.
Y. Bai, Z. Lin, Z. Ye, D. Dong, J. Wang, L. Chen, F. Xie, Y. Li, P. H. Dixneuf, M. Zhang, Org. Lett., 2022, 24, 7988-7992.

Reliable, operationally simple, catalytic α-selective hydroalumination reactions proceed in the presence of diisobutylaluminum hydride and (Ni(dppp)Cl2), and, unlike uncatalyzed transformations, generate little or no alkynylaluminum byproducts. The derived α-vinyl halides and boronates can be synthesized through direct treatment with the appropriate electrophiles.
F. Gao, A. H. Hoveyda, J. Am. Chem. Soc., 2010, 132, 10961-10963.

The reaction of styrylsulfonium salts with zinc powder provides zinc reagents. Transition metals and other additives are not required for promoting zincation. The reaction tolerates a variety of sensitive functional groups, including esters, bromides, and boronic esters, and proceeds with complete retention of stereochemistry.
K. Yamada, M. B. Kintzel, G. J. P. Perry, H. Saito, H. Yorimitsu, Org. Lett., 2022, 24, 7446-7449.

Trapping of a diazo species in an intermolecular fashion by two independent ion species in tandem at the carbene center installs an electrophile and a nucleophile on the same carbon. This metal-free concept enables regioselective syntheses of various vinyl halides, vinyl sulfones, and alkyne derivatives.
D. P. Ojha, K. R. Prabhu, Org. Lett., 2015, 17, 18-21.

β-Oxido phosphonium ylides, generated in situ from aldehydes and Wittig reagents react readily with electrophilic halogen sources to form predominantly or exclusively E-bromo- or iodosubstituted alkenes. The stereochemical outcome on halogenation is remarkably sensitive to alkylidene size [ethylidene(triphenyl)phosphorane is highly Z-selective].
D. M. Hodgson, T. Arif, J. Am. Chem. Soc., 2008, 130, 16500-16501.

An efficient and practical hydroiodination of internal alkynes using ex situ generated HI provides afford (E)-vinyl iodides in good yields under mild conditions. This regio- and stereoselective hydroiodination reaction shows high functional group tolerance toward alkyl, methoxy, halogen, trifluoromethyl, cyano, ester, halomethyl, acid-sensitive silyl ether, and acetal moieties.
K. Nozawa-Kumada, K. Noguchi, T. Akada, M. Shigeno, Y. Kondo, Org. Lett., 2021, 23, 6659-6663.

An efficient protocol for a highly stereoselective one-pot synthesis of (E)-β-aryl vinyl iodides and (E)-β-aryl vinyl bromides from styrenes is based on a ruthenium-catalyzed silylative coupling followed by a N-halosuccinimide-mediated halodesilylation reaction.
P. Pawluć, G. Hreczycho, J. Szudkowska, M. Kubicki, B. Marciniec, Org. Lett., 2009, 11, 3390-3393.

Using triethylamine as catalyst in Hunsdiecker reactions with N-halosuccinimides as Br+ or I+ source, cinnamic acids, and propiolic acids are converted to the corresponding α-halostyrenes and 1-halo-1-alkynes in good isolated yields within 1-5 min.
J. Prakash, S. Roy, J. Org. Chem., 2002, 67, 7861-7864.

A hydroiodation of alkynes using an iodine/hydrophosphine binary system takes place regioselectively to provide the corresponding Markovnikov-type adducts in good yield. This hydroiodation offers mild conditions, convenient operation, and tolerates various functional groups.
S.-i. Kawaguchi, A. Ogawa, Org. Lett., 2010, 12, 1893-1895.

Bromoboration of propyne with BBr3 proceeds in syn-selectivity to produce (Z)-2-bromo-1-propenyldibromoborane, which is prone to stereoisomerization. Treatment with pinacol yields the stable and storable pinacolboronate. Negishi coupling gives trisubstituted (Z)-alkenylpinacolboronates in good yields. Iodinolysis of the boronates affords alkenyl iodides in good yields.
C. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.

The use of ammonium persulfate as an oxidant and iodide as an iodine source enables stereospecific diiodination of alkynes under mild conditions in water. The highly efficient reaction provides a broad range of (E)-diiodoalkenes.
Q. Jiang, J.-Y. Wang, C.-C. Guo, Synthesis, 2015, 47, 2081-2087.

Hypervalent iodine reagents mediate practical oxidative iodinations for the chemoselective mono-, di-, and tri-iodination of alkynes. The reaction conditions were systematically optimized by altering the iodine source and/or the hypervalent iodine reagent system.
Y. Liu, D. Huang, J. Huang, K. Maruoka, J. Org. Chem., 2017, 82, 11865-11871.

Hypervalent iodine reagents mediate practical oxidative iodinations for the chemoselective mono-, di-, and tri-iodination of alkynes. The reaction conditions were systematically optimized by altering the iodine source and/or the hypervalent iodine reagent system.
Y. Liu, D. Huang, J. Huang, K. Maruoka, J. Org. Chem., 2017, 82, 11865-11871.

Unprecedented decompositions of unprotected alkynyl hydrazones provide allenoates via DABCO-promoted Wolff-Kishner reduction, tetrasubstituted α,γ-dihaloallenoates in the presence of N-halosuccinimides, and functionalized tricyclic azepines in the presence of DBU.
P. Jamwal, A. Sharma, R. Gurubrahamam, Org. Lett., 2023, 25, 6607-6612.

The use of 1,3-diiodo-5,5,-dimethylhydantoin and HF-based reagents enables a regio- and stereoselective iodofluorination of internal and terminal alkynes. A facile method for a controlled regioselective double iodofluorination of terminal alkynes is also presented.
L. Pfeifer, V. Gouverneur, Org. Lett., 2018, 20, 1576-1579.

A CuI-catalyzed iodoformylation of terminal alkynes with TMSCF3 and NaI provides (E)-β-iodo-α,β-unsaturated aldehydes with excellent chemoselectivity, regioselectivity, and stereoselectivity. This synthetic method uses inexpensive and easy-to-handle chemical feedstocks. Synthetic applications of the (E)-β-iodo-α,β-unsaturated aldehydes are demonstrated.
D. Lu, X. Yang, W. Guan, S.-F. Yin, N. Kambe, R. Qiu, Org. Lett., 2022, 24, 6993-6998.

An efficient synthesis of α-iodo/bromo-α,β-unsaturated aldehydes/ketones directly from propargylic alcohols is catalyzed collaboratively by Ph3PAuNTf2 and MoO2(acac)2, and Ph3PO as an additive helps suppress undesired enone/enal formation. Notable features of this method include low catalyst loadings, mild reaction conditions, and mostly good diastereoselectivity.
L. Ye, L. Zhang, Org. Lett., 2009, 11, 3646-3649.

A catalytic amount of Au(PPh3)NTf2 converts readily accessible propargylic acetates into versatile linear α-iodoenones in good to excellent yields. Very good Z-selectivities are observed for aliphatic propargylic acetates.
M. Yu, G. Zhang, L. Zhang, Org. Lett., 2007, 9, 2087-2090.

Bis(pyridine) iodonium tetrafluoroborate (Barluenga’s reagent) promotes the rearrangement of propargylic alcohol derivatives under mild conditions to provide β-unsubstituted, β-monosubstituted, and β,β-disubstituted α-iodoenones in high yields. β-Substituted α-iodoenones are obtained with excellent (Z)-selectivity.
T. Suárez-Rodríguez, Á. L. Suárez-Sobrino, A. Ballesteros, J. Org. Chem., 2018, 83, 12575-12583.

An iodo Meyer-Schuster rearrangement of 3-alkoxypropargyl alcohols using iodine or NIS in dichloromethane at ambient temperature produces α-iodo-α,β-unsaturated esters in good yields. Secondary alcohols gave Z-isomers exclusively.
S. Puri, N. Thirupathi, M. S. Reddy, Org. Lett., 2014, 16, 5246-5249.

A regio- and stereoselective iodination, along with some examples for bromination, of readily available acrylamides proceeds under mild conditions via a Rh(III)-catalyzed C-H-activation/halogenation mechanism. The reaction represents a rare example of a direct halogenation of electron-poor acrylic acid derivatives to access a variety of differently substituted Z-haloacrylic acid derivatives.
N. Kuhl, N. Schröder, F. Glorius, Org. Lett., 2013, 15, 3860-3863.

γ-Hydroxy-α,β-acetylenic esters are used as precursors for the preparation of γ-hydroxy-α,β-alkenoic esters by means of trans-selective additions of two hydrogen atoms or one hydrogen atom and one iodine atom across the triple bonds. These methods allow the preparation of β-substituted and α,β-disubstituted alkenoic esters in highly stereoselective manners.
C. T. Meta, K. Koide, Org. Lett., 2004, 6, 1785-1787.

A radical carbozincation of diethyl acetylenedicarboxylate in the presence of air leads to fumaric derivatives through a selective alkylzinc group radical transfer controlled by coordination. The total trans stereocontrol is unprecedented, carbocupration is well-known to give the reversal selectivity at low temperature, while classical radical addition methodologies lead to mixtures of isomers.
J. Maury, L. Feray, M. P. Bertrand, Org. Lett., 2011, 13, 1884-1887.

Various ketones as the electrophiles react in a one pot three-component coupling with an aluminum allenoate intermediate derived from ethyl propiolate and alluminium iodide to yield β-iodo Morita-Baylis-Hillman adducts with high yield and excellent Z-stereoselectivity.
S. Il Lee, G.-S. Hwang, D. H. Ryu, Synlett, 2007, 59-62.

A simple and highly stereoselective method has been developed for the synthesis of (Z)-β-iodo Baylis-Hillman adducts using CeCl3ˇ7H2O/NaI as an inexpensive and readily available reagent system.
J. S. Yadav, B. V. S. Reddy, M. K. Gupta, B. Eeshwaraiah, Synthesis, 2005, 57-60.

Various bis-activated cyclopropenes undergo highly stereoselective ring-opening reactions to produce multisubstituted alkenyl halides in the presence of stoichiometric magnesium halides. Trapping of the magnesium enolate intermediates in situ allows the synthesis of highly functionalized compounds.
Y. Wang, H. W. Lam, J. Org. Chem., 2009, 74, 1353-1355.

A new, diastereoselective three-component halo aldol reaction has been discovered for the tandem formations of I-C/C-C bonds, which gives aldol adducts in good yields. The key intermediates (allenolates and 1-iodo-3-siloxy-1,3-butadienes), were directly monitored by 1H NMR.
H.-X. Wei, S. H. Kim, G. Li, Org. Lett., 2002, 4, 3691-3693.

A new silver-catalyzed highly regio- and stereoselective difunctionalization reaction of simple terminal alkynes gives (Z)-β-haloenol acetate derivatives in good yields. The resulting products are versatile intermediates in organic synthesis.
Z. Chen, J. Li, H. Jiang, S. Zhu, Y. Li, C. Qi, Org. Lett., 2010, 12, 3262-3265.

Poly{[4-(hydroxy)(tosyloxy)iodo]styrene} was efficient in the halotosyloxylation reaction of alkynes with iodine or NBS or NCS. The polymer reagent could be regenerated and reused.
J.-M. Chen, X. Huang, Synthesis, 2004, 1557-1558.

The iodonitration of alkynes with I2 and tBuONO enables a convenient synthesis of β-iodonitro alkenes.
Y. Fan, B. Zhou, K. Chen, B. Wang, X. Li, X. Xu, Synlett, 2017, 28, 1657-1659.

2-Alkynyl esters are stereo- and regioselectively converted to E-β-chloro-α-iodo-α,β-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. Single-isomer tetrasubstituted olefins bearing four different carbon substituents are then synthesized by sequential palladium-catalyzed coupling reactions.
A. B. Lemay, K. S. Vulic, W. W. Ogilvie, J. Org. Chem., 2006, 71, 3615-3618.

(E)-β-Iodo vinylsulfones are synthesized in very good yields under ultrasound irradiation using alkynes, sulfonyl hydrazides, potassium iodide and hydrogen peroxide. The key features of this protocol are the speed and efficiency of the reactions.
C. Zhou, X. Zeng, Synthesis, 2021, 53, 4614-4620.

A mild, electrophilic cyclization of substituted propargylic aryl ethers by I2, ICl, and PhSeBr produces 3,4-disubstituted 2H-benzopyrans in excellent yields. This methodology tolerates various functional groups, such as methoxy, alcohol, aldehyde, and nitro groups.
S. A. Worlikar, T. Kesharwani, T. Yao, R. C. Larock, J. Org. Chem., 2007, 72, 1347-1353.

Iodocyclopentenes are formed at room temperature upon iodonium-promoted 5-endo-dig carbocyclization of δ-alkynyl-β-ketoesters with I2. Cyclizations involving terminal and substituted (alkyl, aryl, Br, I) alkynes were accessed.
J. Barluenga, D. Palomas, E. Rubio, J. M. Gonzáles, Org. Lett., 2007, 9, 2823-2826.

The facile iodolactonisation of ethyl 2,3-allenoates with I2 in aqueous MeCN gave 4-iodofuran-2(5H)-ones in moderate to high yields.
C. Fu, S. Ma, Eur. J. Org. Chem., 2005, 3942-3945.

Lithiation of 1-iodo-1,3-dienyl phosphine oxides and subsequent Wittig-Horner reaction with aldehydes gives vinyl allenes in high yields. The preparation of the 1-iodo-1,3-dienyl phosphine oxides is described. This multi-step sequence allows the synthesis of vinyl allenes from two different alkynes and one aldehyde.
Z. Xi, W.-X. Zhang, Z. Song, W. Zheng, F. Kong, T. Takahashi, J. Org. Chem., 2005, 70, 8785-8789.

The cerium(IV) ammonium nitrate (CAN) mediated reaction of aryl sulfinates and sodium iodide with alkenes afforded vinyl sulfones in very good yields. Alkynes underwent a similar reaction to give β-iodovinyl sulfones, which on treatment with potassium carbonate afforded the corresponding acetylenic sulfones in high yields.
V. Nair, A. Augustine, T. D. Suja, Synthesis, 2002, 2259-2265.