One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate

Ming Chung Yan; Jing Yuan Liu; Wen Wei Lin; Kuo Hsi Kao; Ju Tsung Liu; Jeong Jiunn Jang; Ching Fa Yao

doi:10.1016/S0040-4020(99)00741-3

One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate

Ming Chung Yan, Jing Yuan Liu, Wen Wei Lin, Kuo Hsi Kao, Ju Tsung Liu, Jeong Jiunn Jang, Ching Fa Yao^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

Reaction of β-nitrostyrenes 1 with allyl mercaptan 2 in the presence of triethylamine generated unsaturated nitro sulfides 3 and then the solution was treated with methyl chloroformate (MCF) and was refluxed to obtain [3.3.0]bicyclic products trans-6 and cis-6 in one-pot. The ratios of trans- 6:cis-6 were from 1.1:1 to 1.8:1 and the mechanism of the formation 6 is proposed to proceed through the formation of nitrile oxides 5 to undergo intramolecular nitrile oxide-olefin cycloaddition (INOC). Nitronates 16, prepared from 1 with allyl alcohol and base, can be converted into methoxycarbonyl nitronates 22 by treating the solution with methyl chloroformate and catalytic amount of 4-dimethylaminopyridine (DMAP) in the presence of different amounts of triethylamine. Intermediates 22 can either undergo intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) to generate highly stereoselective product trans-14 or undergo INOC to yield trans-14 and cis-14. The application of this improved methodology to synthesize different heterocyclic products 10, 26, and 27 is reported.

Original language	English
Pages (from-to)	12493-12514
Number of pages	22
Journal	Tetrahedron
Volume	55
Issue number	43
DOIs	https://doi.org/10.1016/S0040-4020(99)00741-3
Publication status	Published - 1999 Oct 22

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Access to Document

10.1016/S0040-4020(99)00741-3

Fingerprint

Dive into the research topics of 'One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate'. Together they form a unique fingerprint.

Cite this

Yan, M. C., Liu, J. Y., Lin, W. W., Kao, K. H., Liu, J. T., Jang, J. J., & Yao, C. F. (1999). One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate. Tetrahedron, 55(43), 12493-12514. https://doi.org/10.1016/S0040-4020(99)00741-3

One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate. / Yan, Ming Chung; Liu, Jing Yuan; Lin, Wen Wei et al.
In: Tetrahedron, Vol. 55, No. 43, 22.10.1999, p. 12493-12514.

Research output: Contribution to journal › Article › peer-review

Yan, MC, Liu, JY, Lin, WW, Kao, KH, Liu, JT, Jang, JJ & Yao, CF 1999, 'One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate', Tetrahedron, vol. 55, no. 43, pp. 12493-12514. https://doi.org/10.1016/S0040-4020(99)00741-3

@article{cdfb7286a20b4642948b5f874ddf5d14,

title = "One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate",

abstract = "Reaction of β-nitrostyrenes 1 with allyl mercaptan 2 in the presence of triethylamine generated unsaturated nitro sulfides 3 and then the solution was treated with methyl chloroformate (MCF) and was refluxed to obtain [3.3.0]bicyclic products trans-6 and cis-6 in one-pot. The ratios of trans- 6:cis-6 were from 1.1:1 to 1.8:1 and the mechanism of the formation 6 is proposed to proceed through the formation of nitrile oxides 5 to undergo intramolecular nitrile oxide-olefin cycloaddition (INOC). Nitronates 16, prepared from 1 with allyl alcohol and base, can be converted into methoxycarbonyl nitronates 22 by treating the solution with methyl chloroformate and catalytic amount of 4-dimethylaminopyridine (DMAP) in the presence of different amounts of triethylamine. Intermediates 22 can either undergo intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) to generate highly stereoselective product trans-14 or undergo INOC to yield trans-14 and cis-14. The application of this improved methodology to synthesize different heterocyclic products 10, 26, and 27 is reported.",

author = "Yan, {Ming Chung} and Liu, {Jing Yuan} and Lin, {Wen Wei} and Kao, {Kuo Hsi} and Liu, {Ju Tsung} and Jang, {Jeong Jiunn} and Yao, {Ching Fa}",

note = "Funding Information: Financial support by the National Science Council of the Republic of China (Grant NSC 89-2113-M-003-001) is gratefully acknowledged.",

year = "1999",

month = oct,

day = "22",

doi = "10.1016/S0040-4020(99)00741-3",

language = "English",

volume = "55",

pages = "12493--12514",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "43",

}

TY - JOUR

T1 - One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate

AU - Yan, Ming Chung

AU - Liu, Jing Yuan

AU - Lin, Wen Wei

AU - Kao, Kuo Hsi

AU - Liu, Ju Tsung

AU - Jang, Jeong Jiunn

AU - Yao, Ching Fa

N1 - Funding Information: Financial support by the National Science Council of the Republic of China (Grant NSC 89-2113-M-003-001) is gratefully acknowledged.

PY - 1999/10/22

Y1 - 1999/10/22

N2 - Reaction of β-nitrostyrenes 1 with allyl mercaptan 2 in the presence of triethylamine generated unsaturated nitro sulfides 3 and then the solution was treated with methyl chloroformate (MCF) and was refluxed to obtain [3.3.0]bicyclic products trans-6 and cis-6 in one-pot. The ratios of trans- 6:cis-6 were from 1.1:1 to 1.8:1 and the mechanism of the formation 6 is proposed to proceed through the formation of nitrile oxides 5 to undergo intramolecular nitrile oxide-olefin cycloaddition (INOC). Nitronates 16, prepared from 1 with allyl alcohol and base, can be converted into methoxycarbonyl nitronates 22 by treating the solution with methyl chloroformate and catalytic amount of 4-dimethylaminopyridine (DMAP) in the presence of different amounts of triethylamine. Intermediates 22 can either undergo intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) to generate highly stereoselective product trans-14 or undergo INOC to yield trans-14 and cis-14. The application of this improved methodology to synthesize different heterocyclic products 10, 26, and 27 is reported.

AB - Reaction of β-nitrostyrenes 1 with allyl mercaptan 2 in the presence of triethylamine generated unsaturated nitro sulfides 3 and then the solution was treated with methyl chloroformate (MCF) and was refluxed to obtain [3.3.0]bicyclic products trans-6 and cis-6 in one-pot. The ratios of trans- 6:cis-6 were from 1.1:1 to 1.8:1 and the mechanism of the formation 6 is proposed to proceed through the formation of nitrile oxides 5 to undergo intramolecular nitrile oxide-olefin cycloaddition (INOC). Nitronates 16, prepared from 1 with allyl alcohol and base, can be converted into methoxycarbonyl nitronates 22 by treating the solution with methyl chloroformate and catalytic amount of 4-dimethylaminopyridine (DMAP) in the presence of different amounts of triethylamine. Intermediates 22 can either undergo intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) to generate highly stereoselective product trans-14 or undergo INOC to yield trans-14 and cis-14. The application of this improved methodology to synthesize different heterocyclic products 10, 26, and 27 is reported.

UR - http://www.scopus.com/inward/record.url?scp=0033595873&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033595873&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(99)00741-3

DO - 10.1016/S0040-4020(99)00741-3

M3 - Article

AN - SCOPUS:0033595873

SN - 0040-4020

VL - 55

SP - 12493

EP - 12514

JO - Tetrahedron

JF - Tetrahedron

IS - 43

ER -

One-pot synthesis of five-membered cyclic thioethers or ethers via intramolecular nitrile oxide-olefin cycloaddition (INOC) or intramolecular alkoxycarbonyl nitronate-olefin cycloaddition (IAOC) by the use of methyl chloroformate

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this