220018-33-7Relevant academic research and scientific papers
Synthesis of Sulfones and Sulfonyl Derivatives using Sodium (tert-butyldimethylsilyl)oxymethanesulfinate
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Paragraph 0836-0841; 0843; 0845-0846; 0848-0851; 0883-0886, (2021/04/29)
The present invention relates to a method for manufacturing a sulfone and sulfonyl derivative compound using sodium (tert-butyldimethylsilyl)oxymethanesulfinate, which is a novel organic sulfin salt, wherein the novel organic sulfin salt has good stability, environmental friendliness and economy, and is easy to handle, and thus significantly reduces the amount of transition metal catalysts and the amount of organic sulfin salts used when introducing aryl or alkenyl. Also, alkylation, arylation, amination, and fluorination are all possible during secondary functionalization. Therefore, the present invention can be usefully used in preparation and mass production of various kinds of sulfones and derivatives thereof including asymmetric sulfone derivatives.
Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives
Kim, Dae-Kwon,Um, Hyun-Suk,Park, Hoyoon,Kim, Seonwoo,Choi, Jin,Lee, Chulbom
, p. 13071 - 13078 (2021/01/09)
An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO22-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.
Formal synthesis of borrelidin: A highly enantio- and diastereoselective access to the Morken's C2-C12 intermediate
Gembus, Vincent,Karmazin, Lydia,Uguen, Daniel,Zoller, Thomas
, p. 359 - 380 (2019/02/25)
In contrast to methyl and isobutyl phenyl sulfone, condensing under basic conditions higher alkyl sulfones and trans-2,3-epoxy-butanol 13c (or its O-benzyl and O-silyl derivatives) proved unfeasible, a difficulty that was overcome by using mono ethers of trans-2,3-epoxy-butane-1,4-diol 35c as the electrophilic reagents. Thus, adding excess BuLi to a mixture of the benzyl ether 35b and sulfone ent-12a, a stereodiad sulfone prepared in pure state from the R-Roche ester, via the O-trityloxy-sulfone ent-12c (X-ray), gave, after elimination by column chromatography of the side-formed regioisomer, a diolsulfone that was next converted to sulfone 20 by means of conventional functional-group modifications. Reacting like-wise this sulfone with the parent O-PMB derivative 35a, and then proceeding to the same purification process and function adjustment, delivered the title fragment in virtually pure state.
Total synthesis of polycavernoside A, a lethal toxin of the red alga Polycavernosa tsudai
Blakemore, Paul R.,Browder, Cindy C.,Hong, Jian,Lincoln, Christopher M.,Nagornyy, Pavel A.,Robarge, Lonnie A.,Wardrop, Duncan J.,White, James D.
, p. 5449 - 5460 (2007/10/03)
Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)-3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-ζ-hydroxy-α,β-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.
Baker's yeast mediated biohydrogenation of sulphur-functionalised methacrolein derivatives. Stereochemical aspects of the reaction and preparation of the two enantiomers of useful C4 bifunctional chiral synthons
Serra, Stefano,Fuganti, Claudio
, p. 2191 - 2196 (2007/10/03)
The baker's yeast mediated reduction of sulphur-functionalised methacroleins 11, 15 and 18 leads to the preparation of the bifunctional methyl branched C4 chiral synthons 6 and 7. The stereochemical aspects of the biohydrogenation have been investigated. Both the oxidation state of sulphur and the isomeric position of the double bond affected the enantioselectivity of the reduction strongly, thus, offering access to the two enantiomeric forms of 6 and 7.
Approaches to a synthesis of galbonolide B
Smith, Peter M.,Thomas, Eric J.
, p. 3541 - 3556 (2007/10/03)
An approach to the C(7)-C(15) fragment of galbonolide B 2 has been completed in which the diene fragment 51 was assembled from (R)-3-tert-butyldimethylsilyloxypentan-2-one 29 by conversion into the unsaturated ester 30, acylation of the sulfone 47 using this ester, reductive desulfurisation, methylenation using a Wittig reaction and deprotection. Following model studies, the aldehyde 62, prepared by oxidation of the alcohol 51, was converted into a mixture of the epimeric alcohols 63 and these were converted into the di(methylene)tridecadienoic acid 65 using a phosphine catalysed Ireland-Claisen rearrangement. Sharpless epoxidations of the alcohol 67 using either L-(+)- or D-(-)-diethyl tartrate were highly stereoselective and gave the epoxides 68 and 69 which were clearly distinguishable. Model studies using the heptadiene monoepoxide 70 led to a synthesis of the monoprotected dihydroxy aldehyde 76 so establishing a protocol for the introduction into the vicinal diol of the galbonolides. Finally, aldol addition of tert-butyl acetate to the aldehyde 78 followed by selective protection, deprotection and cyclisation completed a synthesis of the macrolide 85.
Toward a total synthesis of an aglycone of spiramycin; installation of the hydroxy groups at C-4 and C-5: A model study
Oddon,Uguen,De Cian,Fischer
, p. 1149 - 1152 (2007/10/03)
The stereochemical course of the osmium-mediated bis-hydroxylation of the allylic derivative 6c, whose the structure is closely related to that of a C-1/C-7 fragment of the title aglycone, has been established unambiguously by X-ray analysis of a carboxylic[ic acid derived from one of the two diastereomeric diols which formed.
