東華大學圖書館 |

語系: 繁體中文

說明(常見問題)

回圖書館首頁

手機版館藏查詢

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

New Strategies for Stereo- and Regio...

Miller, Zachary D.

FindBook

Google Book

Amazon

博客來

New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation./
作者:	Miller, Zachary D.
面頁冊數:	214 p.
附註:	Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.
Contained By:	Dissertation Abstracts International76-09B(E).
標題:	Organic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3701828
ISBN:	9781321727364

New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation.
Miller, Zachary D.

New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation. - 214 p.

Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.

Thesis (Ph.D.)--University of Michigan, 2015.

Controlling the regiochemistry in additions of silanes across units of unsaturation is a significant challenge in route to important stereo- and regiodefined alkenyl- and allylsilane intermediates. In many cases the absence of substrate biases or appended directing groups, these reactions are unselective affording mixtures of inseparable constitutional isomers. With the aim to develop catalyst-controlled strategies to find solutions for these challenges, we investigated allene hydrosilylations due to the possibility of accessing either allyl- or alkenylsilanes from one substrate class.

ISBN: 9781321727364Subjects--Topical Terms:

523952
Organic chemistry.

New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation.
LDR:03570nmm a2200289 4500 001 2067683
005 20160418090147.5
008 170521s2015 ||||||||||||||||| ||eng d
020 $a 9781321727364
035 $a (MiAaPQ)AAI3701828
035 $a AAI3701828
040 $a MiAaPQ $c MiAaPQ
100 1 $a Miller, Zachary D. $3 3182542
245 1 0 $a New Strategies for Stereo- and Regiocontrol in Allene Hydrosilylation.
300 $a 214 p.
500 $a Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.
500 $a Adviser: John Montgomery.
502 $a Thesis (Ph.D.)--University of Michigan, 2015.
520 $a Controlling the regiochemistry in additions of silanes across units of unsaturation is a significant challenge in route to important stereo- and regiodefined alkenyl- and allylsilane intermediates. In many cases the absence of substrate biases or appended directing groups, these reactions are unselective affording mixtures of inseparable constitutional isomers. With the aim to develop catalyst-controlled strategies to find solutions for these challenges, we investigated allene hydrosilylations due to the possibility of accessing either allyl- or alkenylsilanes from one substrate class.
520 $a Regioselective allene hydrosilylations with N-heterocyclic carbene (NHC) complexes of nickel and palladium have been developed and are described. In this reaction manifold, regioselectivity is governed primarily by choice of metal as alkenylsilanes are produced via nickel catalysis with larger NHC ligands and allylsilanes are produced via palladium catalysis with smaller NHC ligands. These complementary methods allow either regioisomeric product to be obtained with exceptional regiocontrol. Additional complementary access to the corresponding alkenylsilanes is accomplished with palladium catalysis via a novel ligand-controlled strategy with a class of large NHC ligands. In this approach, modification of NHC ligand structure from a common palladium pre-catalyst permits either regioisomeric product to be afforded in excellent regiocontrol via the reversal of a palladium hydrometalation to a silylmetalation. As an extension of this discovery, a one-pot hydroarylation protocol has been elucidated to afford functionalized branched alkene isomers. This process involves regioselective allene hydrosilylation in tandem with a palladium-catalyzed cross-coupling reaction to furnish exclusively functionalized 1,1-disubstituted olefins.
520 $a Regio- and stereocontrolled additions to 1,3-disubstituted allenes affording either E-allylsilanes with palladium NHC catalysts or Z-alkenylsilanes with nickel NHC catalysts have been discovered. It was found that a variety of symmetrically and unsymmetrical 1,3-disubstituted allenes were tolerated with the optimized reaction conditions. The NHC nickel catalyst developed selectively affords only the Z-stereoisomer, which is typically the opposite stereochemistry experienced in normal mode transition-metal catalyzed hydrometalations. In addition, when the nickel reaction was conducted with unsymmetrical allenes differentiated by steric encumbrance result in only one isomer was afforded in high yields. These developments provide access to important stereo- and regiodefined, metalated intermediates useful in a variety of synthetic transformations.
590 $a School code: 0127.
650 4 $a Organic chemistry. $3 523952
690 $a 0490
710 2 $a University of Michigan. $b Chemistry. $3 2101148
773 0 $t Dissertation Abstracts International $g 76-09B(E).
790 $a 0127
791 $a Ph.D.
792 $a 2015
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3701828