Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles

Surendra Thapa, Roshan K. Dhungana, Rajani Thapa Magar, Bijay Shrestha, Shekhar Kc, Ramesh Giri

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.

Original languageEnglish (US)
Pages (from-to)904-909
Number of pages6
JournalChemical Science
Volume9
Issue number4
DOIs
StatePublished - Jan 1 2018

Fingerprint

Alkenes
Biological Products
Hydrides

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Thapa, Surendra ; Dhungana, Roshan K. ; Magar, Rajani Thapa ; Shrestha, Bijay ; Kc, Shekhar ; Giri, Ramesh. / Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles. In: Chemical Science. 2018 ; Vol. 9, No. 4. pp. 904-909.
@article{e26adbdecfc54b58aff6ae634e01adb0,
title = "Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles",
abstract = "We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.",
author = "Surendra Thapa and Dhungana, {Roshan K.} and Magar, {Rajani Thapa} and Bijay Shrestha and Shekhar Kc and Ramesh Giri",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c7sc04351a",
language = "English (US)",
volume = "9",
pages = "904--909",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "4",

}

Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles. / Thapa, Surendra; Dhungana, Roshan K.; Magar, Rajani Thapa; Shrestha, Bijay; Kc, Shekhar; Giri, Ramesh.

In: Chemical Science, Vol. 9, No. 4, 01.01.2018, p. 904-909.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles

AU - Thapa, Surendra

AU - Dhungana, Roshan K.

AU - Magar, Rajani Thapa

AU - Shrestha, Bijay

AU - Kc, Shekhar

AU - Giri, Ramesh

PY - 2018/1/1

Y1 - 2018/1/1

N2 - We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.

AB - We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.

UR - http://www.scopus.com/inward/record.url?scp=85041205282&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85041205282&partnerID=8YFLogxK

U2 - 10.1039/c7sc04351a

DO - 10.1039/c7sc04351a

M3 - Article

C2 - 29629157

AN - SCOPUS:85041205282

VL - 9

SP - 904

EP - 909

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 4

ER -