Glycosyl Sulfoxides in Glycosylation Reactions

Zeng, Jing; Liu, Yan; Chen, Wei; Zhao, Xin; Meng, Lingkui; Wan, Qian

doi:10.1007/s41061-018-0205-4

Cited by 41 publications

(15 citation statements)

References 124 publications

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“…Later, a detailed optimization of the sulfoxide unit and more applications of this reaction were reported, 76,77 and recently the use of sulfoxides in carbohydrate synthesis has been reviewed. 78,79…”

Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

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Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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“…Seeking much higher β ‐selectivity, we shifted to the sulfoxide 17 , featuring an anomeric leaving group never used before in HAD. In this case, 17 (1.7 equiv) was activated using Tf 2 O in CH 2 Cl 2 at −70 °C in the presence of 18 , DTBMP, and ADMB, which resulted in the formation of the desired 19 with high facial selectivity ( α / β :1/20) and in 64 % yield. To verify that this glycosylation took place through HAD, we did a control experiment using the donor 17′ , an analogue of 17 whose picoloyl was replaced by a benzoyl.…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of Tiacumicin B: Implementing Hydrogen Bond Directed Acceptor Delivery for Highly Selective β‐Glycosylations

et al. 2020

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A total synthesis of tiacumicin B, a natural macrolide whose remarkable antibiotic properties are used to treat severe intestinal infections, is reported. The strategy is in part based on the prior synthesis of the tiacumicin B aglycone, and on the decisive use of sulfoxides as anomeric leaving groups in hydrogen‐bond‐mediated aglycone delivery (HAD). This new HAD variant permitted highly β‐selective rhamnosylation and noviosylation. To increase convergence, the rhamnosylated C1–C3 fragment thus obtained was anchored to the C4–C19 aglycone fragment by adapting the Suzuki–Miyaura cross‐coupling used for the aglycone synthesis. Ring‐size‐selective macrolactonization provided a compound engaged directly in the noviolysation step with virtually total β selectivity. The final efficient removal of all the protecting groups provided synthetic tiacumicin B.

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“…was first examined in CH2Cl2 at -50 °C using Tf2O in the presence of the acceptor 17, 2,6-di-terbutyl-4-methylpiridine (DTBMP) as acid scavenger, and 4-allyl-1,2-dimethoxybenzene (ADMB) ( Table 1, entry 8). 36,37 We were pleased to find that under these conditions the desired glycosylated compound 19 with an upgraded facial selectivity (a/b : 1/12) and a yield of 52%. Higher yield (70%) and selectivity (a/b : 1/20) could be further attained by increasing the donor amount (2.1 eq.)…”

Section: Preparation Of the Eastern Part With 2-o-methyl-d-rhamnosementioning

confidence: 99%

Total Synthesis of Tiacumicin B: Study of the Challenging β‐Selective Glycosylations**

Tresse

François-Heude

Servajean

et al. 2021

Chemistry A European J

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We report here a full account of the total synthesis of tiacumicin B (Tcn-B), a natural glycosylated macrolide with remarkable antibiotic properties. Our strategy is based on our experience with the synthesis of the tiacumicin B aglycone and on unique 1,2-cisglycosylation steps. It features the conclusive use of sulfoxide anomeric leaving-groups in combination with a remote 3-O-picoloyl group on the donors allowing highly b-selective rhamnosylation and noviosylation that rely on H-bond-mediated Aglycone Delivery (HAD). The rhamnosylated C1-C3 fragment was anchored to the C4-C19 aglycone fragment by a Suzuki-Miyaura cross-coupling. Ring-size selective Shiina macrolactonization provided a semi-glycosylated aglycone that was engaged directly in the noviolysation step with a virtually total b-selectivity. Finally, a novel deprotection method was devised for the removal of a 2-naphthylmethylidene (Nap) ether on a phenol and efficient removal of all the protecting groups provided synthetic tiacumicin B.

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Glycosyl Sulfoxides in Glycosylation Reactions

Cited by 41 publications

References 124 publications

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Total Synthesis of Tiacumicin B: Implementing Hydrogen Bond Directed Acceptor Delivery for Highly Selective β‐Glycosylations

Total Synthesis of Tiacumicin B: Study of the Challenging β‐Selective Glycosylations**

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