Modular Construction of Protected 1,2/1,3-Diols, -Amino Alcohols, and -Diamines via Catalytic Asymmetric Dehydrative Allylation: An Application to Synthesis of Sphingosine

Tanaka, Shinji; Ramachandran, Gunasekar; Tanaka, Tatsuya; Iyoda, Yoko; Suzuki, Yusuke; Kitamura, Masato

doi:10.1021/acs.joc.7b01181

Cited by 16 publications

(10 citation statements)

References 54 publications

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“…Apparently, our protocol describes a reasonable methodology for the conversion of epoxides to protected 1,2-diols and 2-amino alcohols. Attention is drawn on these 1,2-oxygen and/or nitrogen units since they are present in natural products ranging from small molecules, such as sugars, lipids and amino acids to huge molecules [56].…”

Section: Resultsmentioning

confidence: 99%

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

Demir¹,

Sarı²,

Çetinkaya³

et al. 2020

Beilstein J. Org. Chem.

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The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained in ratios close to 1:1 in the cyclization reactions. The best yields of these compounds were obtained in dichloromethane (DCM). Together with 16 known compounds, two novel oxazolidinone derivatives and two novel cyclic carbonates were synthesized with an efficient and straightforward method. Compared to the existing methods, the synthetic approach presented here provides the following distinct advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated. The further investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates disclosed that the cycloaddition reaction proceeds via an asynchronous concerted mechanism in gas phase and in DCM.

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Section: Resultsmentioning

confidence: 99%

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

Demir¹,

Sarı²,

Çetinkaya³

et al. 2020

Beilstein J. Org. Chem.

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“…The catalysis has been extended to the cyclization of allylic alcohols with unstable acetals, hemiaminals, hemiaminal ethers, or aminals for the one‐step construction of methylene‐bridged chiral modules of 1,2‐ and 1,3‐O and/or N function(s) [20] …”

Section: Cpru‐pyridinecarboxylic Acid Systemmentioning

confidence: 99%

Asymmetric Dehydrative Allylation Using Soft Ruthenium and Hard Brønsted Acid Combined Catalyst

Tanaka

Kitamura

2021

The Chemical Record

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Asymmetric Pd‐catalyzed Tsuji‐Trost‐type allylation is an important catalytic reaction toward chiral natural and unnatural product syntheses. We successfully modified a desalt‐type reaction using allyl ester or halide to a dehydrative one using allylic alcohol via the establishment of two redox‐mediated donor acceptor bifunctional catalyst systems. These systems were cationic CpRu‐Cl‐Napy‐PyCOOH and cationic CpRu‐Naph‐diPIM‐dioxo‐iPr/p‐TsOH and were designed on the basis of the soft ruthenium and hard Brønsted acid combined catalyst concept. The complementary use of the two chiral catalysts for dehydrative asymmetric allylation expands the application scope facilitating the utilization of both aliphatic and aromatic allylic alcohols with various nucleophiles in the substrate. In this account, the design, synthesis, and application of these catalysts were reported.

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“…[18] m.p. 43 ℃); [17] Method B: To a solution of compound 4a (150 mg, 0.39 mmol) in 6 mL of dried DCM was added 0.6 mL of dried pyridine and Tf 2 O (0.15 mL, 0.89 mmol) at -20 ℃ under a nitrogen atmosphere. After the disappearance of the starting material, the solution was concentrated in vacuo.…”

Section: Synthesis Of (2s3r4e)-2-azido-13-o-benzylidene-4-octa-decmentioning

confidence: 99%

“…Besides, we developed a novel protocol for the synthesis of azidosphingosine from L-arabinose. Though D-arabinose has been used as chiral pool to synthesize D-erythro-sphingosine in the previous literature, [17] in which E-selective Wittig olefination was employed as key step. To the best of our knowledge, this is the first report about the synthesis of azidosphingosine from L-arabinose.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Azidosphingosine from D-Galactose or L-Arabinose

高阳光¹,

曹周²,

韩忠享³

et al. 2019

Chin. J. Org. Chem.

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Modular Construction of Protected 1,2/1,3-Diols, -Amino Alcohols, and -Diamines via Catalytic Asymmetric Dehydrative Allylation: An Application to Synthesis of Sphingosine

Cited by 16 publications

References 54 publications

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

Asymmetric Dehydrative Allylation Using Soft Ruthenium and Hard Brønsted Acid Combined Catalyst

Synthesis of Azidosphingosine from D-Galactose or L-Arabinose

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