Unusual rearrangement–remercuration reactions of allylic silanols

Nagamalla, Someshwar; Dhokale, Ranjeet A.; Seidl, Frederick J.; Mague, Joel T.; Sathyamoorthi, Shyam

doi:10.1039/d1qo01008e

Cited by 14 publications

(13 citation statements)

References 37 publications

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“…Temporary tethering using Lewis acid templates affords excellent regiocontrol with epoxides, − but only one such report exists with aziridines . Our laboratory has a programmatic focus on the development of the di- tert -butyl-silanol auxiliary into a uniquely reactive functional handle. − We envisioned a ring opening of aziridines by pendant di- tert -butyl silanol auxiliaries, which would afford protected amino alcohols in a single transformation. Here, we show our development of this reaction, and its application in the rapid assembly of select natural products and analogues.…”

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Ring Opening of Aziridines by Pendant Silanols Allows for Preparations of (±)-Clavaminol H, (±)-Des-Acetyl-Clavaminol H, (±)-Dihydrosphingosine, and (±)-N-Hexanoyldihydrosphingosine

et al. 2022

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We present a unique strategy for the synthesis of vicinal amino alcohols. Ring opening of aziridines with pendant silanols is compatible with a range of substrates. To engage productively in ring opening, the aziridine must be at least mildly activated, and a variety of such N-substituents are tolerated. The utility of this methodology is highlighted in facile preparations of the natural products (±)-Clavaminol H, (±)-dihydrosphingosine, and (±)-N-hexanoyldihydrosphingosine as well as a natural product analogue (±)-des-acetyl-Clavaminol H.

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Ring Opening of Aziridines by Pendant Silanols Allows for Preparations of (±)-Clavaminol H, (±)-Des-Acetyl-Clavaminol H, (±)-Dihydrosphingosine, and (±)-N-Hexanoyldihydrosphingosine

et al. 2022

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“…Our laboratory is deeply invested in exploring di- tert -butylsilanols as covalent tethers for the intramolecular installation of hydroxy groups. − The triol motif is prevalent in a variety of carbohydrate and polyketide natural products with attractive biological activity (Figure ). We envisioned a ring-opening reaction of epoxides by pendant di- tert -butylsilanols, which would form a variety of protected triols in a single transformation.…”

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Ring Opening of Epoxides by Pendant Silanols

2022

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We present a new ring-opening reaction of epoxides by pendant silanols, catalyzed by either Ph 3 C + BF 4 − or BINOLphosphoric acid. Silanol epoxides derived from trans-allylic alcohols, cis-allylic alcohols, trans-homoallylic alcohols, and cishomoallylic alcohols were all compatible and gave products from either endo-or exo-ring opening. With silanol epoxides derived from 4-alkenyl silanols, an unusual rearrangement to tetrahydrofuran products was observed. The utility of this methodology was demonstrated in a short preparation of protected D-arabitol.

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“…In such processes, controlling the regioselectivity of nucleophilic attack is often a challenge. “Tethering” a desired nucleophile to an existing functional group in the molecule of interest allows for intramolecular attack, which often proceeds with predictable regioselectivity and high diastereocontrol. − Our laboratory has provided the first examples of the use of silanol tethers for the intramolecular ring opening of both transient and stable electrophiles. − …”

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Hydroxyselenylation and Tethered Silanoxyselenylation of Allylic Silanols

Joshi

Sathyamoorthi

2022

J. Org. Chem.

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We present protocols for the highly regioselective hydroxyselenylation and silanoxyselenylation of allylic silanols. N-(Phenylseleno)phthalimide acts as the selenylating agent for both transformations. Under basic conditions, hydroxyselenylation proceeds with >20:1 regioselectivity, and the products are valuable synthons for further transformations. We show that the silanol plays a critical role in maintaining the yield and regioselectivity of this reaction. Surprisingly, under acidic conditions, the hydroxyselenylation pathway is blocked, and products of a tethered silanoxyselenylation are exclusive.

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Unusual rearrangement–remercuration reactions of allylic silanols

Abstract: We present the first examples of rearrangement reactions of allylic silanol substrates into linear ketone and 5-membered cyclic silanediol organomercurial products. Both reactions are mediated by Hg(OTf)2 but differ in...

Cited by 14 publications

References 37 publications

Ring Opening of Aziridines by Pendant Silanols Allows for Preparations of (±)-Clavaminol H, (±)-Des-Acetyl-Clavaminol H, (±)-Dihydrosphingosine, and (±)-N-Hexanoyldihydrosphingosine

Ring Opening of Aziridines by Pendant Silanols Allows for Preparations of (±)-Clavaminol H, (±)-Des-Acetyl-Clavaminol H, (±)-Dihydrosphingosine, and (±)-N-Hexanoyldihydrosphingosine

Ring Opening of Epoxides by Pendant Silanols

Hydroxyselenylation and Tethered Silanoxyselenylation of Allylic Silanols

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