Silicon and phosphinomethanides: Novel heteroelement substituted methanes and yields

Hans Heinz Karsch; Roland Richter

doi:10.1002/9783527619894.ch24

Silicon and phosphinomethanides: Novel heteroelement substituted methanes and yields

Hans Heinz Karsch
, Roland Richter

Natural Sciences

Technical University of Munich

Research output: Chapter in Book/Report/Conference proceeding › Chapter › peer-review

1 Scopus citations

Abstract

LiCH(PMe₂)₂ reacts with SiC1₄ or with PhR₂SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe₂)₂(SiMe₂Ph) is deprotonated by nBuLi to give trimeric (Li[C(PMe₂)₂(SiMe₂Ph)])₂. (Li[C(PMe₂)(SiMe₃)₂])₂.TMEDA 3 reacts with RR'SiCl₂ via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC1₃ with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl₃ (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

Original language	English
Title of host publication	Organosilicon Chemistry II
Subtitle of host publication	From Molecules to Materials
Publisher	Wiley Blackwell
Pages	187-193
Number of pages	7
ISBN (Electronic)	9783527619894
ISBN (Print)	9783527292547
DOIs	https://doi.org/10.1002/9783527619894.ch24
State	Published - 25 Apr 2008

Keywords

Carbanion nucleophilicity
Heterocycles
Phosphinomethanes
Silicon-phosphorus bonds
Tetraheteroatom

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10.1002/9783527619894.ch24

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title = "Silicon and phosphinomethanides: Novel heteroelement substituted methanes and yields",

abstract = "LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric (Li[C(PMe2)2(SiMe2Ph)])2. (Li[C(PMe2)(SiMe3)2])2.TMEDA 3 reacts with RR'SiCl2 via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where {"}C{"}-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl3 (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.",

keywords = "Carbanion nucleophilicity, Heterocycles, Phosphinomethanes, Silicon-phosphorus bonds, Tetraheteroatom",

author = "Karsch, \{Hans Heinz\} and Roland Richter",

note = "Publisher Copyright: {\textcopyright} 1996 VCH Verlagsgesellschaft mbH.",

year = "2008",

month = apr,

day = "25",

doi = "10.1002/9783527619894.ch24",

language = "English",

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pages = "187--193",

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TY - CHAP

T1 - Silicon and phosphinomethanides

T2 - Novel heteroelement substituted methanes and yields

AU - Karsch, Hans Heinz

AU - Richter, Roland

PY - 2008/4/25

Y1 - 2008/4/25

N2 - LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric (Li[C(PMe2)2(SiMe2Ph)])2. (Li[C(PMe2)(SiMe3)2])2.TMEDA 3 reacts with RR'SiCl2 via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl3 (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

AB - LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric (Li[C(PMe2)2(SiMe2Ph)])2. (Li[C(PMe2)(SiMe3)2])2.TMEDA 3 reacts with RR'SiCl2 via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl3 (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

KW - Carbanion nucleophilicity

KW - Heterocycles

KW - Phosphinomethanes

KW - Silicon-phosphorus bonds

KW - Tetraheteroatom

UR - https://www.scopus.com/pages/publications/84955717607

U2 - 10.1002/9783527619894.ch24

DO - 10.1002/9783527619894.ch24

M3 - Chapter

AN - SCOPUS:84955717607

SN - 9783527292547

SP - 187

EP - 193

BT - Organosilicon Chemistry II

PB - Wiley Blackwell

ER -

Silicon and phosphinomethanides: Novel heteroelement substituted methanes and yields

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