Frustrated Lewis pair addition to conjugated diynes: Formation of zwitterionic 1,2,3-butatriene derivatives

被引：26

作者：

Feldhaus, Philipp ^{[1
]}

Schirmer, Birgitta ^{[1
]}

Wibbeling, Birgit ^{[1
]}

Daniliuc, Constantin G. ^{[1
]}

Froehlich, Roland ^{[1
]}

Grimme, Stefan ^{[2
]}

Kehr, Gerald ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

[2] Univ Bonn, Inst Phys & Theoret Chem, Mulliken Ctr Theoret Chem, D-53115 Bonn, Germany

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 30期

关键词：

PHOSPHINES; REACTIVITY; ACTIVATION; COMPLEXES; BORANE; CO2;

D O I：

10.1039/c2dt30321c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The frustrated Lewis pair B(C6F5)(3)/P(o-tolyl)(3) (4a) reacts with 4,6-decadiyne to give the trans-1,2-addition product 5. In contrast, the B(C6F5)(3)/(PBu3)-Bu-t FLP (4b) reacts with this substrate to give the trans-1,4-adduct trans-6. The cumulene trans-6 undergoes trans-/cis-isomerization upon photolysis to give a ca. 1 : 1 trans-6/cis-6 mixture. The FLP 4b reacts with 2,6-hexadiyne at r.t. to yield a ca. 4 : 1 mixture of their trans-1,2- and trans-1,4-addition products (7,8). DFT calculations showed that the zwitterionic 1,4-addition products are favored under thermodynamic control. Thermolysis of the kinetic trans-1,2-addition product (7) (80 degrees C, bromobenzene) does not lead to the thermodynamically favored 1,4-isomer (8), but instead elimination of isobutylene occurs to the formal trans-1,2-adduct (9) of the B(C6F5)(3)/(PHBu2)-Bu-t pair. Compounds 5, 6, 7, 8, 9 were analyzed by X-ray diffraction.

引用

页码：9135 / 9142

页数：8

共 57 条

[1]

Ahlrichs R., 2010, TURBOMOLE VERSION 6

[2]

[Anonymous], 2010, ANGEW CHEM-GER EDIT

[3] Exchange-hole dipole moment and the ospersion interaction [J].

Becke, AD ;

Johnson, ER .

JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (15)

[4] Chloro- and phenoxy-phosphines in frustrated Lewis pair additions to alkynes [J].

Caputo, Christopher B. ;

Geier, Stephen J. ;

Ouyang, Eva Y. ;

Kreitner, Christoph ;

Stephan, Douglas W. .

DALTON TRANSACTIONS, 2012, 41 (01) :237-242

[5] Exploring the Limits of Frustrated Lewis Pair Chemistry with Alkynes: Detection of a System that Favors 1,1-Carboboration over Cooperative 1,2-P/B-Addition [J].

Chen, Chao ;

Eweiner, Florian ;

Wibbeling, Birgit ;

Froehlich, Roland ;

Senda, Shunsuke ;

Ohki, Yasuhiro ;

Tatsumi, Kazuyuki ;

Grimme, Stefan ;

Kehr, Gerald ;

Erker, Gerhard .

CHEMISTRY-AN ASIAN JOURNAL, 2010, 5 (10) :2199-2208

[6] Remarkably variable reaction modes of frustrated Lewis pairs with non-conjugated terminal diacetylenes [J].

Chen, Chao ;

Froehlich, Roland ;

Kehr, Gerald ;

Erker, Gerhard .

CHEMICAL COMMUNICATIONS, 2010, 46 (20) :3580-3582

[7] Deprotonation and Addition Reactions of Frustrated Lewis Pairs with Alkynes [J].

Dureen, Meghan A. ;

Brown, Christopher C. ;

Stephan, Douglas W. .

ORGANOMETALLICS, 2010, 29 (23) :6594-6607

[8] Terminal Alkyne Activation by Frustrated and Classical Lewis Acid/Phosphine Pairs [J].

Dureen, Meghan A. ;

Stephan, Douglas W. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (24) :8396-+

[9] P-C Bond Activation Chemistry: Evidence for 1,1-Carboboration Reactions Proceeding with Phosphorus-Carbon Bond Cleavage [J].

Ekkert, Olga ;

Kehr, Gerald ;

Froehlich, Roland ;

Erker, Gerhard .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (12) :4610-4616

[10] Organometallic frustrated Lewis pair chemistry [J].

Erker, Gerhard .

DALTON TRANSACTIONS, 2011, 40 (29) :7475-7483

← 1 2 3 4 5 6 →