scispace - formally typeset
Journal ArticleDOI: 10.1002/ANIE.202101947

Direct Allylic C(sp3)−H and Vinylic C(sp2)−H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light

04 Mar 2021-Angewandte Chemie (John Wiley & Sons, Ltd)-Vol. 60, Iss: 21, pp 11779-11783
Abstract: Direct allylic C-H thiolation is straightforward for allylic C(sp3 )-S bond formation. However, strong interactions between thiol and transition metal catalysts lead to deactivation of the catalytic cycle or oxidation of sulfur atom under oxidative condition. Thus, direct allylic C(sp3 )-H thiolation has proved difficult. Represented herein is an exceptional for direct, efficient, atom- and step-economic thiolation of allylic C(sp3 )-H and thiol S-H under visible light irradiation. Radical trapping experiments and electron paramagnetic resonance (EPR) spectroscopy identified the allylic radical and thiyl radical generated on the surface of photocatalyst quantum dots (QDs). The C-S bond formation does not require external oxidants and radical initiators, and hydrogen (H2 ) is produced as byproduct. When vinylic C(sp2 )-H was used instead of allylic C(sp3 )-H bond, the radical-radical cross-coupling of C(sp2 )-H and S-H was achieved with liberation of H2 . Such a unique transformation opens up a door toward direct C-H and S-H coupling for valuable organosulfur chemistry.

... read more

Topics: Allylic rearrangement (59%)
Citations
  More

6 results found


Journal ArticleDOI: 10.1039/D1QO01076J
Zhanqun Liang1, Kang Lv1, Shaofang Zhou1, Changlei Zhu1  +1 moreInstitutions (1)
Abstract: Herein, we disclose a protocol to synthesize trisubstituted alkenyl thioethers through a direct S-alkylation of 1,2,3-thiadiazoles with C-radical precursors, 4-alkyl-1,4-dihydropyridines (DHPs), driven by visible-light photocatalysis. A broad range of primary, secondary, and tertiary C-radical precursors, DHPs, are suitable for this reaction and the desired products can be obtained in good to excellent yields under mild conditions. Remarkably, high stereoselectivity with Z-alkenyl thioethers was achieved in the presence of a Cu(OAc)2 catalyst. Synergistic experimental and computational studies were carried out to shed light on the mechanisms of this reaction, in which the quenching pathway of an excited photocatalyst (*RuII) could be altered in the presence of the Cu(OAc)2 catalyst. A reductive quenching pathway (RuII/*RuII/RuI/RuII) is proposed in the absence of the Cu(OAc)2 catalyst while an oxidative quenching pathway (RuII/*RuII/RuIII/RuII) is suggested with the assistance of the Cu(OAc)2 catalyst. In addition, the origin of the Z-selectivity of the product is discussed.

... read more

1 Citations


Journal ArticleDOI: 10.1002/ANIE.202109849
Li-Zhu Wu1, Jia Qiao, Zi-Qi Song, Cheng Huang  +4 moreInstitutions (1)
18 Sep 2021-Angewandte Chemie
Abstract: As one of the most ubiquitous bulk reagents available, the intrinsic chemical inertness of tetrahydrofuran (THF) makes direct and site-selective C(sp 3 )-H bond activation difficult, especially under redox neutral condition. Here, we demonstrate that semiconductor quantum dots (QDs) can activate α-C-H bond of THF via forming QDs/THF conjugates. Under visible light irradiation, the resultant alkoxyalkyl radical directly engages in radical cross-coupling with α-amino radical from amino C-H bonds or radical addition with alkene or phenylacetylene, respectively. In contrast to stoichiometric oxidant or hydrogen atom transfer reagents required in previous studies, the scalable benchtop approach can execute α-C-H bond functionalization of THF only by a QD photocatalyst under redox-neutral condition, thus providing a broad of value added chemicals starting from bulk THFs reagent. The high step- and atom-economy, high efficiency and broad substrate scope make the photocatalysis with QDs and visible light promising in both academic and industrial setting.

... read more

Topics: Alkene (53%), Photocatalysis (50%)

Journal ArticleDOI: 10.1002/ANIE.202112370
Yuan-Yuan Cheng1, Ji-Xin Yu1, Tao Lei1, Hong-Yu Hou1  +3 moreInstitutions (1)
29 Sep 2021-Angewandte Chemie
Abstract: 1,4-Dicarbonyl compounds are intriguing motifs and versatile precursors in numerous pharmaceutical molecules and bioactive natural compounds. Direct incorporation of two carbonyl groups into a double bond at both ends is straightforward, but also challenging. Represented herein is the first example of 1,2-dicarbonylation of alkenes by photocatalysis. Key to success is that N(n-Bu)4 + not only associates with the alkyl anion to avoid protonation, but also activates the α-keto acid to undergo electrophilic addition. The α-keto acid is employed both for acyl generation and electrophilic addition. By tuning the reductive and electrophilic ability of the acyl precursor, unsymmetric 1,4-dicarbonylation is achieved for the first time. This metal-free, redox-neutral and regioselective 1,2-dicarbonylation of alkenes is executed by a photocatalyst for versatile substrates under extremely mild conditions and shows great potential in biomolecular and drug molecular derivatization.

... read more

Topics: Electrophilic addition (61%), Double bond (52%), Protonation (52%) ... show more

Open accessJournal ArticleDOI: 10.1039/D1SC03667J
Tao Li1, Kangjiang Liang1, Jiaying Tang1, Yuzhen Ding1  +2 moreInstitutions (1)
21 Oct 2021-Chemical Science
Abstract: Thiophenol was discovered to form an EDA complex with iodobenzene through halogen bonding interactions upon treatment with KOH. A direct photochemical thiolation of C(sp3)–H bond-containing etheric, allylic, and benzylic substrates with thiophenol was developed. The reaction proceeded on the basis of the in situ generation of a thiyl radical and aryl radical through single electron transfer between the photoexcited thiophenolate anion and aryl iodide EDA complex. Then a C(sp3) centred-radical was formed by aryl radical-mediated hydrogen atom transfer and the thiolation products were delivered via a radical–radical cross-coupling with the thiyl radical.

... read more

Topics: Aryl radical (57%), Iodobenzene (56%), Thiophenol (55%) ... show more

Journal ArticleDOI: 10.1002/CSSC.202101504
Jianing Li1, Jingnan Zhao1, Cunfei Ma1, Zongyi Yu1  +3 moreInstitutions (1)
19 Nov 2021-Chemsuschem
Abstract: The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104 ). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51-84 % yields and TONs up to 3.4×104 . The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.

... read more

Topics: Chemical reaction (52%)

References
  More

60 results found


Journal ArticleDOI: 10.1021/CR020027W
Barry M. Trost1, Matthew L. Crawley1Institutions (1)
21 Jun 2003-Chemical Reviews
Abstract: A. Primary Alcohols as Nucleophiles 2931 B. Carboxylates as Nucleophiles 2931 C. Alkylations with Phenols 2932 IV. Nitrogen Nucleophiles in AAA Total Synthesis 2935 A. Alkylamines as Nucleophiles 2935 B. Azides as a Nucleophile 2936 C. Sulfonamide Nucleophiles 2937 D. Imide Nucleophiles 2938 E. Heterocyclic Amine Nucleophiles 2940 V. Sulfur Nucleophiles 2941 VI. Summary and Conclusions 2941 VII. Acknowledgment 2941 VIII. References 2942 I. Considerations for Enantioselective Allylic Alkylation

... read more

Topics: Allylic rearrangement (58%), Total synthesis (53%), Tsuji–Trost reaction (53%) ... show more

2,021 Citations


Journal ArticleDOI: 10.1016/S0891-5849(87)80033-3
Abstract: Spin trapping has become a valuable tool for the study of free radicals in biology and medicine. The electron spin resonance hyperfine splitting constants of spin adducts of interest in this area are tabulated. The entries also contain a brief comment on the source of the radical trapped.

... read more

Topics: Spin trapping (64%), Zero field splitting (60%), Hyperfine structure (55%) ... show more

1,361 Citations



Journal ArticleDOI: 10.1021/CR9902749
Teruyuki Kondo and1, Take-aki Mitsudo1Institutions (1)
11 Jul 2000-Chemical Reviews
Topics: Triple bond (61%), Bond order (60%), Single bond (59%) ... show more

1,059 Citations


Journal ArticleDOI: 10.1021/CR400441M
02 Jan 2014-Chemical Reviews
Abstract: s a hydrogen atom from the thiol to give hydroperoxide 96 and a thiyl radical, which propagates the chain. Hydroperoxide 96 is reduced in the presence of triphenyl phosphine to give the corresponding alcohol 91. The preference for the formation of cis-3,5-disubstituted 1,2-dioxolanes is in agreement with the Beckwith−Houk transition state model for 5-exo-trig cyclizations. Similarly, the addition of thiophenol onto 5methylhepta-1,3,6-triene 97 under an atmosphere of oxygen led to 1,2-dioxolane 98, isolated in 49% as a single diastereoisomer after treatment with triphenyl phosphine, together with minor amounts of linear alcohols 99 and 100 (Scheme 49, eq b). This reaction is remarkable for a number of reasons. First, the addition of the thiyl radical occurs exclusively at the terminal position of the conjugated diene system and not at the terminal alkene, thus highlighting the higher reactivity of conjugated dienes as compared to isolated alkenes. Second, intermolecular trapping of the resulting allyl radical is reversible and regioselective under these reaction conditions. Because of the reversibility of the reaction between the allyl radical and molecular oxygen, both ratios 1,4/1,2-addition and 1,2dioxolane/linear alcohols strongly depend upon the initial concentration in thiol. Accordingly, the 1,2-dioxolanes were obtained in good yields only in highly diluted solutions. Finally, the 5-exo-trig cyclization occurs in a completely stereoselective manner, with only one of the two diastereomeric peroxyl radical intermediates (101) undergoing cyclization, while the other one (102) either leads to linear alcohol 99 or fragments back the allyl radical (Scheme 49, eq b). The reversible reaction of allyl radicals with molecular oxygen was also demonstrated for carotenoid-derived carbon-centered radical generated by Scheme 47 Scheme 48. Application to the Preparation of Functionalized 1,2,4-Trioxanes Chemical Reviews Review dx.doi.org/10.1021/cr400441m | Chem. Rev. XXXX, XXX, XXX−XXX X addition of a thiyl radical to the conjugated polyene carotene. This process has been extended to include the more challenging 1,5-dienes, from which six-membered ring endoperoxides can be obtained. Bachi and co-workers applied the thiol−olefin cooxidation process to the total synthesis of antimalarial agent yingzhaosu A (Scheme 50) and its C14epimer, as well as the preparation of a series of active analogues, from readily available limonene 103. The overall process is extremely challenging in this case due to the particular structure of the diene, with the 6-exo-cyclization process being in competition with intermolecular hydrogen atom abstraction from the thiol, and also potentially with intramolecular hydrogen abstraction from the activated allylic position by the reactive oxygen-centered radical. As previously observed, addition of the thiyl radical takes place at the less hindered position, and due to the lack of stereocontrol during the trapping of the resulting carbon-centered radical, peroxyl radical 105 is formed as a 1:1 mixture of diastereoisomers (Scheme 50). The latter undergoes 6-exo-trig cyclization to give carbon-centered radical 106. Unlike the initial trapping with molecular oxygen, the 2,3-dioxabicyclo[3.3.1]nonane system of 106 allows a highly diastereoselective reaction for the second trapping with molecular oxygen from the less hindered face to give 107. Alcohol 104 is then obtained following hydrogen abstraction from the thiol by peroxyl radical 107 and reduction of the resulting hydroperoxide with triphenylphosphine. The yields of endoperoxides remain relatively low (ca. 20−30%, calculated on the diene); however, considering the accessibility and the cost of the reactants (thiophenol, limonene, and oxygen), this approach represents a very attractive access to these structurally complex endoperoxides, some of which exhibit very promising activity for the treatment of malaria. 3.3.2. Intramolecular Trapping of the Carbon-Centered Radical. 3.3.2.a. Fragmentation Reaction: RingOpening of Vinyl Cyclopropanes. The carbon-centered radicals generated by addition of a thiyl radical onto the C C bond of vinylcypropanes have been shown to undergo cyclopropane ring-opening. The resulting radical species can then be trapped by hydrogen abstraction from the thiol. This fragmentation is a very fast process with rate constants in the range 10−10 s−1 (310 K) for most of the cyclopropylcarbinyl radicals, which allows for the fragmentation process to compete favorably with intermolecular reactions, as well as with most intramolecular processes. Alternatively, the carboncentered radical resulting from the β-fragmentation of the cyclopropylmethyl radical can engage further in carbon−carbon bond-forming processes. The allylsulfide moiety allows for the addition of radicals with concomitant release of a thiyl radical, and very elegant processes using only substoichiometric amounts of a source of thiyl radicals have been developed for the rearrangement of vinylcyclopropanes (see section 5.2.1.e). In particular, under nonreducing conditions and in the presence of an external olefin, efficient annulation reactions have been achieved, giving access to polycyclic compounds. The carboncentered radicals generated by the thiol-mediated ring-opening Scheme 49 Scheme 50 Chemical Reviews Review dx.doi.org/10.1021/cr400441m | Chem. Rev. XXXX, XXX, XXX−XXX Y of vinylcyclopropanes could also be trapped to form a new carbon−heteroatom bond. Here again, annulations taking advantage of the allylsulfide moiety have been developed (see section 5.2.1.e). Landais, Renaud, and co-workers used vinyl cyclopentenes such as 108, easily prepared by monocyclopropanation of silylcyclopentadienes, as radical acceptors for photogenerated thiyl radicals. The reversible addition of the thiyl radical onto the CC bond of 108 leads eventually to cyclopropylcarbinyl radical 110, which undergoes fragmentation to give carboncentered radical 111, stabilized by the neighboring ester group. Hydrogen atom abstraction from the thiol then furnishes cyclopentene 109 and regenerates a thiyl radical that propagates the chain (Scheme 51, eq a). The addition of the thiyl radical at the β-carbon center takes place in a highly stereoselective manner, opposite to the bulky silyl group. The fate of the stabilized carbon-centered radical resulting from the fragmentation process depends upon the reaction conditions. For instance, Naito and co-workers reported the use of vinylcylopropyl oxime ethers such as 112 in domino reactions promoted by a thiol or a disulfide in the presence of triethylborane. The ring-opening of the cyclopropyl moiety is initiated by addition of a thiyl radical onto the terminal position of vinylcyclopropyl oxime ether 112. The stabilized carboncentered radical resulting from the fragmentation process reacts with triethylborane to form a boryl enamine 115 (Scheme 51, eq b). Depending on the reaction conditions, the latter can engage further in a radical oxygenation process, leading eventually to α-hydroxy oxime ether 113 after reduction of peroxyl radical 116 by the thiol (Scheme 51, eq b). Alternatively, 113 can react with aldehydes in an ionic aldol process to give β-hydroxy oxime ethers in a stereoselective manner, as illustrated by the preparation of 117 from 112 (Scheme 51, eq c). In the aforementioned reactions, the allylsulfide moieties generated upon addition of a thiyl radical onto the vinylcyclopropane unit remain intact at the end of the reaction. However, radical reactions taking advantage of the fragmentation of allyl sulfides upon addition of radical species are also well documented. Some examples of intermolecular additions, as well as cyclization and annulation processes, will be described in section 5.2.1.e. 3.3.2.b. Rearrangement and Cyclization of Nonconjugated Dienes. In the addition of thiyl radicals onto nonconjugated dienes, the CC bonds can either react independently or lead to rearrangements through intramolecular trapping of the carbon-centered radical generated in the initial addition step. In many cyclic dienes, addition occurs selectively at the more strained double bond, and products resulting from rearrangements are often observed. For example, the addition of thiophenol to 5-methylene-norbornene led to the exo addition products 118 and 119, together with tricyclic adduct 120. The latter results from the rearrangement of homoallyl radical intermediate 121 into cyclopropylcarbinyl radical 122 (Scheme 52). Similar rearrangements have been observed in norbornadiene derivatives where substitution at C-7 can influence facial selectivity, while substitution of the methylene bridge in 7,7-dimethylnorbornene proved to have no effect in directing the addition of thiophenol. The formation of cyclopropylcarbinyl radical intermediates in norbornadiene derivatives can also lead to other skeletal rearrangements, as illustrated by the addition of thiophenol to hexachloronorbornadiene 123, which results in the formation of 125, beside the expected 1:1 addition product 124 (Scheme 53, eq a). Following addition of the thiyl radical, presumably from the less hindered endo-face, and subsequent 3-exo-trig cyclization onto the neighboring CC bond, cyclopropylcarbinyl radical 126 undergoes fragmentation to give the more stable α-chlorosubScheme 51 Scheme 52 Chemical Reviews Review dx.doi.org/10.1021/cr400441m | Chem. Rev. XXXX, XXX, XXX−XXX Z stituted carbon-centered radical 127. The latter then abstracts a hydrogen atom from the thiol to give 125 (relative configuration not established) and a thiyl radical, which goes on to propagate the chain. Similar rearrangement was observed i n t h e add i t i on o f t BuSH on to 1 , 2 , 3 , 4 , 7 , 7 hexamethylbicyclo[2.2.1]heptadiene. Likewise, Hodgson and co-workers have observed complete skeletal rearrangements in the addition of thiophenol to 7-azabicyclo[2.2.1]heptadienes such as 128 (Scheme 53, eq b). Transa

... read more

Topics: Organic synthesis (59%)

523 Citations