Acceleration effects of phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds

Masahito Murai, Hirotaka Takeshima, Haruka Morita, Yoichiro Kuninobu, Kazuhiko Takai

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp3)-H bond. The unprecedented catalytic germylation of C(sp3)-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.

Original languageEnglish
Pages (from-to)5407-5414
Number of pages8
JournalJournal of Organic Chemistry
Volume80
Issue number11
DOIs
Publication statusPublished - Jun 5 2015

Fingerprint

phosphine
Rhodium
Ligands
Dehydrogenation
Hydrogen

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Acceleration effects of phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. / Murai, Masahito; Takeshima, Hirotaka; Morita, Haruka; Kuninobu, Yoichiro; Takai, Kazuhiko.

In: Journal of Organic Chemistry, Vol. 80, No. 11, 05.06.2015, p. 5407-5414.

Research output: Contribution to journalArticle

Murai, Masahito ; Takeshima, Hirotaka ; Morita, Haruka ; Kuninobu, Yoichiro ; Takai, Kazuhiko. / Acceleration effects of phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. In: Journal of Organic Chemistry. 2015 ; Vol. 80, No. 11. pp. 5407-5414.
@article{0fe7bc3cc30943c3a71023d22b475455,
title = "Acceleration effects of phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds",
abstract = "The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp3)-H bond. The unprecedented catalytic germylation of C(sp3)-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.",
author = "Masahito Murai and Hirotaka Takeshima and Haruka Morita and Yoichiro Kuninobu and Kazuhiko Takai",
year = "2015",
month = "6",
day = "5",
doi = "10.1021/acs.joc.5b00920",
language = "English",
volume = "80",
pages = "5407--5414",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - Acceleration effects of phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds

AU - Murai, Masahito

AU - Takeshima, Hirotaka

AU - Morita, Haruka

AU - Kuninobu, Yoichiro

AU - Takai, Kazuhiko

PY - 2015/6/5

Y1 - 2015/6/5

N2 - The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp3)-H bond. The unprecedented catalytic germylation of C(sp3)-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.

AB - The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp3)-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp3)-H bond. The unprecedented catalytic germylation of C(sp3)-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.

UR - http://www.scopus.com/inward/record.url?scp=84930631159&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84930631159&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.5b00920

DO - 10.1021/acs.joc.5b00920

M3 - Article

AN - SCOPUS:84930631159

VL - 80

SP - 5407

EP - 5414

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 11

ER -