Isotope Effects, Dynamic Matching, and Solvent Dynamics in a Wittig Reaction. Betaines as Bypassed Intermediates

被引：72

作者：

Chen, Zhuo ^{[1
]}

Nieves-Quinones, Yexenia ^{[1
]}

Waas, Jack R. ^{[1
]}

Singleton, Daniel A. ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 38期

关键词：

EXPERIMENTAL TRANSITION-STATE; SELECTIVITY; MECHANISM; STEPWISE;

D O I：

10.1021/ja506497b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of the Wittig reaction of anisaldehyde with a stabilized ylide was studied by a combination of C-13 kinetic isotope effects, conventional calculations, and molecular dynamics calculations in a cluster of 53 THF molecules. The isotope effects support a cycloaddition mechanism involving two sequential transition states associated with separate C-C and P-O bond formations. However, the betaine structure in between the two transition states is bypassed as an equilibrated intermediate in most trajectories. The role of the dynamics of solvent equilibration in the nature of mechanistic intermediates is discussed.

引用

收藏

页码：13122 / 13125

页数：4

相关论文

共 28 条

[1] Dynamics-driven reaction pathway in an intramolecular rearrangement [J].

Ammal, SC ;

Yamataka, H ;

Aida, M ;

Dupuis, M .

SCIENCE, 2003, 299 (5612) :1555-1557

[2] Nucleophilicity Parameters for Phosphoryi-Stabilized Carbanions and Phosphorus Ylides: Implications for Wittig and Related Olefination Reactions [J].

Appel, Roland ;

Loos, Robert ;

Mayr, Herbert .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (02) :704-714

[3] Concerted transition state, stepwise mechanism. dynamics effects in C2-C6 enyne allene cyclizations [J].

Bekele, T ;

Christian, CF ;

Lipton, MA ;

Singleton, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (25) :9216-9223

[4]

Bell R.P., 1980, TUNNEL EFFECT CHEM, P60

[5] Synchronous or asynchronous? An ''experimental'' transition state from a direct comparison of experimental and theoretical kinetic isotope effects for a Diels-Alder reaction [J].

Beno, BR ;

Houk, KN ;

Singleton, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (41) :9984-9985

[6] THE RELATIVE REACTION VELOCITIES OF ISOTOPIC MOLECULES [J].

BIGELEISEN, J .

JOURNAL OF CHEMICAL PHYSICS, 1949, 17 (08) :675-678

[7] The modern interpretation of the Wittig reaction mechanism [J].

Byrne, Peter A. ;

Gilheany, Declan G. .

CHEMICAL SOCIETY REVIEWS, 2013, 42 (16) :6670-6696

[8] Unequivocal Experimental Evidence for a Unified Lithium Salt-Free Wittig Reaction Mechanism for All Phosphonium Ylide Types: Reactions with β-Heteroatom-Substituted Aldehydes Are Consistently Selective for cis-Oxaphosphetane-Derived Products [J].

Byrne, Peter A. ;

Gilheany, Declan G. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (22) :9225-9239

[9] DYNAMIC MATCHING - THE CAUSE OF INVERSION OF CONFIGURATION IN THE [1,3] SIGMATROPIC MIGRATION [J].

CARPENTER, BK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (23) :6336-6344

[10] Stepwise and concerted electron-transfer/bond breaking reactions.: Solvent control of the existence of unstable π ion radicals and of the activation barriers of their heterolytic cleavage [J].

Costentin, C ;

Robert, M ;

Savéant, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (51) :16834-16840