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Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate

S. Antony Savarimuthu, Leo Prakash Orcid Logo, S. Augustine Thomas, Thirumanavelan Gandhi, Mrinal K. Bera

Organic & Biomolecular Chemistry, Volume: 18, Issue: 18, Pages: 3552 - 3562

Swansea University Author: Leo Prakash Orcid Logo

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DOI (Published version): 10.1039/d0ob00083c

Abstract

DBU mediated 5-exo-dig cyclization of isothiocyanate and propargyl alcohol leading to valuable heterocyclic compounds has been accomplished. The different modes of nucleophilicity (either S-selective or N-selective) of isothiocyanates were found to depend on the substitution pattern of propargyl alc...

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Published in: Organic & Biomolecular Chemistry
ISSN: 1477-0520 1477-0539
Published: Royal Society of Chemistry (RSC) 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa54303
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spelling 2020-06-19T10:16:19.8947042 v2 54303 2020-05-22 Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate bd72868c48af6c0b04bf9f6bb48ce324 0000-0002-8812-8927 Leo Prakash Leo Prakash true false 2020-05-22 MTLS DBU mediated 5-exo-dig cyclization of isothiocyanate and propargyl alcohol leading to valuable heterocyclic compounds has been accomplished. The different modes of nucleophilicity (either S-selective or N-selective) of isothiocyanates were found to depend on the substitution pattern of propargyl alcohol. The terminal propargyl alcohol and isothiocyanate underwent an N-nucleophilic attack to afford 3-substituted 4-methylene oxazolidine-2-thiones. In contrast, exclusive S-nucleophilic cyclization was observed with internal propargyl alcohol to produce (Z)-1,3-oxathiol-2-ylidenes and (Z)-N-(Z)-4-ethylidene-1,3-oxathiolan-2-ylidenes from secondary and primary propargyl alcohols, respectively. The formation of high Z-selectivity in the imine motif and alkene is the highlight of this new method as multiple selectivities over C[double bond, length as m-dash]N and C[double bond, length as m-dash]C in a single system are synthetically highly challenging. The Z-selectivity in imine and alkene may be attributed to electronic and steric factors respectively. Journal Article Organic & Biomolecular Chemistry 18 18 3552 3562 Royal Society of Chemistry (RSC) 1477-0520 1477-0539 14 5 2020 2020-05-14 10.1039/d0ob00083c COLLEGE NANME Materials Science and Engineering COLLEGE CODE MTLS Swansea University 2020-06-19T10:16:19.8947042 2020-05-22T10:06:02.2111691 S. Antony Savarimuthu 1 Leo Prakash 0000-0002-8812-8927 2 S. Augustine Thomas 3 Thirumanavelan Gandhi 4 Mrinal K. Bera 5 54303__17535__35d959ef984f421ea7b0aad587c993e6.pdf 54303.pdf 2020-06-18T13:43:25.0034993 Output 1226202 application/pdf Accepted Manuscript true 2021-04-07T00:00:00.0000000 true English
title Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
spellingShingle Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
Leo Prakash
title_short Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
title_full Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
title_fullStr Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
title_full_unstemmed Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
title_sort Highly Z-selective synthesis of 1,3-oxathiol-2-ylidenes and 4-methylene-oxazolidine-2-thiones via atom-specific 5-exo-dig cyclization of propargyl alcohol with isothiocyanate
author_id_str_mv bd72868c48af6c0b04bf9f6bb48ce324
author_id_fullname_str_mv bd72868c48af6c0b04bf9f6bb48ce324_***_Leo Prakash
author Leo Prakash
author2 S. Antony Savarimuthu
Leo Prakash
S. Augustine Thomas
Thirumanavelan Gandhi
Mrinal K. Bera
format Journal article
container_title Organic & Biomolecular Chemistry
container_volume 18
container_issue 18
container_start_page 3552
publishDate 2020
institution Swansea University
issn 1477-0520
1477-0539
doi_str_mv 10.1039/d0ob00083c
publisher Royal Society of Chemistry (RSC)
document_store_str 1
active_str 0
description DBU mediated 5-exo-dig cyclization of isothiocyanate and propargyl alcohol leading to valuable heterocyclic compounds has been accomplished. The different modes of nucleophilicity (either S-selective or N-selective) of isothiocyanates were found to depend on the substitution pattern of propargyl alcohol. The terminal propargyl alcohol and isothiocyanate underwent an N-nucleophilic attack to afford 3-substituted 4-methylene oxazolidine-2-thiones. In contrast, exclusive S-nucleophilic cyclization was observed with internal propargyl alcohol to produce (Z)-1,3-oxathiol-2-ylidenes and (Z)-N-(Z)-4-ethylidene-1,3-oxathiolan-2-ylidenes from secondary and primary propargyl alcohols, respectively. The formation of high Z-selectivity in the imine motif and alkene is the highlight of this new method as multiple selectivities over C[double bond, length as m-dash]N and C[double bond, length as m-dash]C in a single system are synthetically highly challenging. The Z-selectivity in imine and alkene may be attributed to electronic and steric factors respectively.
published_date 2020-05-14T04:08:52Z
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