Benzothiazole Sulfinate: A Sulfinic Acid Transfer Reagent under Oxidation-Free Conditions

Day, Jacob J.; Neill, Deshka L.; Xu, Shi; Xian, Ming

doi:10.1021/acs.orglett.7b01693

Cited by 43 publications

(46 citation statements)

References 34 publications

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“…This could be accomplished in high yields either by first converting alcohol 1 a to the corresponding phthalimide ( 12 a ) followed by in situ hydrazine deprotection (Scheme A), or by displacement of 1a with di‐ tert ‐butyl‐iminodicarboxylate, followed by deprotection with TFA (Scheme B). A one‐pot conversion of alcohol 1 a to the corresponding sulfones ( 24 a or 25 a ) can similarly be achieved in high yields through SO 2 F 2 ‐mediated sulfide formation followed by oxidation …”

Section: Methodsmentioning

confidence: 99%

“…Ao ne-pot conversion of alcohol 1a to the corresponding sulfones (24 a or 25 a)c an similarly be achievedi nh igh yields through SO 2 F 2mediated sulfide formationf ollowed by oxidation. [23,24] Overall, we have demonstrated the first example of an efficient method for SO 2 F 2 -mediated activation and substitution of aliphatic alcohols. Thisp rotocol allows the formation of CÀN and CÀSb onds starting from aw ide range of alcohols, including the bioactivem olecules tropicamide and cortexolone.…”

mentioning

confidence: 99%

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One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

Epifanov

Hodgson

et al. 2020

Chemistry A European J

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The Mitsunobu reaction is ap owerful transformation for the one-pota ctivation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein,w er eport ap hosphine free methodf or alcohola ctivationand substitution that is mediated by sulfuryl fluoride. This new method is effective for aw ide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatict hiol nucleophilesi n7 4% average yield. Activatedc arbon nucleophilesa nd ad eactivated phenolw ere also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % averagey ield with enantiomeric ratios up to 99:1. This new protocol has ad istinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. Thisf eature was exploitedi n severale xamples that did not require chromatographyf or purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This methoda lso provides ab oarder nucleophile scope comparedt oe xisting phosphine-free methods.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

Epifanov

Hodgson

et al. 2020

Chemistry A European J

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“…It is important to mention here that sulfinic acids are inherently unstable and are usually prepared freshly or in situ. 65 To the best of our knowledge, we report here for the first time the in situ conversion of SBT to BS and successful trapping of an unstable BS intermediate in a stable caesium complex (2).…”

Section: Solution Characterizationmentioning

confidence: 87%

New s‐block complexes of 1,10‐phenanthroline and 1,3‐benzothizole‐2‐thiolate inhibit ureasein silicoandin vitro

Shah

Khiat

et al. 2020

Applied Organom Chemis

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The coordination chemistry of 1,10‐phenanthroline (phen) and sodium 1,3‐benzothiazole‐2‐thiolate (SBT) with selected s‐block elements has been investigated. Four metal complexes were prepared and their structures were characterized using a variety of analytical techniques including infrared, UV–visible, 1H NMR and 13C NMR spectroscopies, elemental analysis, mass spectrometry and single‐crystal X‐ray diffraction. The reactions of phen and SBT with M(X)n (M = K(I), Cs(I), Mg(II), Sr(II); X = OH−, CO3−, Cl−; n = 1, 2) in MeOH–H2O yielded one‐dimensional chains of both potassium [K2(phen)2(BT)2(H2O)4]n (1) and caesium [Cs(phen)(BS)(H2O)]n (2) (where BT = 1,3‐benzthiazole‐2‐thiolate and BS = 1,3‐benzthiazole‐2‐sulfinothiolate) and mononuclear complexes of both magnesium {[Mg(phen)(H2O)4](BT)2·phen} (3) and strontium {[Sr(phen)2(H2O)4](BT)2} (4). In these complexes, phen binds via an N,N′ chelate pocket, while the monoanonic BT− ligands either coordinate in a bidentate fashion (in the case of 1) or remain uncoordinated (in the case of 3 and 4). In complex 2, SBT ligand was oxidized in situ into a new BS ligand. The sulfinothiolate oxygen atoms in BS coordinate with caesium in a tridentate fashion. Complexes 1–4 were evaluated against urease for enzyme inhibition. The complexes displayed significant inhibition with IC50 values in the range 10.8–45.8 μM. In order to examine the structure–activity relationship, the complexes were docked at the active site of urease. Docking results clearly demonstrate the binding of each complex within the active site of the enzyme.

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“…1 H NMR (600 MHz, CDCl3) δ 7.63-7.52 (m, 5H), 5.61 (dtt, J = 15.4, 6.3, 1.4 Hz, 1H), 5.44 (dtt, J = 15.2, 6.8, 1.6 Hz, 1H), 3.45 (t, J = 7.3 Hz, 2H), 2.54 (qd, J = 7.2, 1.2 Hz, 2H), 2.03 (dtdd, J = 8.9, 7.5, 6.2, 1.3 Hz, 2H), 0.98 (t, J = 7.5 Hz, 3H). 13 C NMR (150 MHz,CDCl3) δ 154.54,135.47,133.89,130.20,129.90,125.56,124.00,33.49,32.23,25.65,13. The title compound was prepared on a 0.300 mmol scale according to General Procedure 1. The crude residue was purified by SiO2 gel column chromatography (5% Et2O/hexanes).…”

Section: (E)-(hex-3-en-1-ylsulfinyl)benzene ((E)-i-c)mentioning

confidence: 99%

“…1 H NMR (600 MHz, CDCl3) δ 5.55 (dtt, J = 15.3, 6.2, 1.4 Hz, 1H), 5.40 (dtt, J = 15.1, 6.7, 1.6 Hz, 1H), 4.21 (t, J = 7.9 Hz, 2H), 3.37 (t, J = 7.9 Hz, 2H), 3.13 (t, J = 7.4 Hz, 2H), 2.38 (q, J = 6.5 Hz, 2H), 2.01 (dq, J = 7.7, 6.1 Hz, 2H), 0.96 (t, J = 7.5 Hz, 3H). 13 C NMR (150 MHz, CDCl3) δ 165. 80, 134.60, 126.33, 64.48, 35.49, 32.88, 32.43, 25.67, 13. 5.58-5.50 (m, 1H), 5.44-5.36 (m, 1H), 3.36 (td, J = 7.3, 1.4 Hz, 2H), 2.50-2.41 (m, 2H), 2.03-1.88 (m, 2H), 0.93 (td, J = 7.3, 2.8 Hz, 3H).…”

Section: (E)-(hex-3-en-1-ylsulfinyl)benzene ((E)-i-c)mentioning

confidence: 99%

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

Romine¹,

Yang²,

Karunananda³

et al. 2019

Preprint

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A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accomplish with traditional strongly coordinating directing groups. This benzothiazole thioether, (BT)S, directing group can be used to promote oxidative Heck reactivity of internal alkenes providing a wide range of products in moderate to high yields. To demonstrate the broad applicability of this directing group, arene C–H olefination was also successfully developed. Reaction progress kinetic analysis provides insights into the role of the directing group in each reaction, which is supplemented with computational data for the oxidative Heck reaction. Furthermore, this (BT)S directing group can be transformed into a number of synthetically useful functional groups, including a sulfone for Julia olefination, allowing it to serve as a “masked olefin” directing group in synthetic planning. In order to demonstrate this synthetic utility, natural products (+)-salvianolic acid A and salvianolic acid F are formally synthesized using the (BT)S directed C–H olefination as the key step.

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Benzothiazole Sulfinate: A Sulfinic Acid Transfer Reagent under Oxidation-Free Conditions

Cited by 43 publications

References 34 publications

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

One‐Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

New s‐block complexes of 1,10‐phenanthroline and 1,3‐benzothizole‐2‐thiolate inhibit ureasein silicoandin vitro

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

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