Chirality of the trisubstituted nitrogen center - XRD, dynamic NMR, and DFT investigation of 1,2-dihydrobenzo[e][1,2,4]triazine derivatives

被引：4

作者：

Kaszynski, Piotr ^{[1
,2
,3
]}

Klys, Arkadiusz ^{[2
]}

Domagala, Slawomir ^{[4
]}

Wozniak, Krzysztof ^{[4
]}

机构：

[1] Polish Acad Sci, Ctr Mol & Macromol Studies, Sienkiewicza 112, PL-90363 Lodz, Poland

[2] Univ Lodz, Dept Chem, Tamka 12, PL-91403 Lodz, Poland

[3] Middle Tennessee State Univ, Dept Chem, Murfreesboro, TN 37132 USA

[4] Univ Warsaw, Dept Chem, Pasteura 5, PL-02089 Warsaw, Poland

来源：

TETRAHEDRON | 2017年 / 73卷 / 27-28期

关键词：

Chirality; Dynamic NMR; Heterocyclic chemistry; Single crystal XRD; DFT calculations; CONFORMATIONAL RATE-PROCESSES; ASYMMETRIC NITROGEN; CONFIGURATIONAL STABILITY; MOLECULAR-STRUCTURE; HINDERED INVERSION; GEMINAL SYSTEMS; N BOND; HYDRAZINES; RESOLUTION; BARRIERS;

D O I：

10.1016/j.tet.2017.05.032

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Molecular structures of two 1-aryl-2-benzyloxycarbonyl-1,2-dihydrobenzo[e][1,2,4]triazines 1 were established by single crystal XRD and compared to those of 4-benzyloxycarbonyl (2) and 4-benzyl (4) analogues. The structures revealed a highly pyramidalized asymmetric N(1) center stabilized by steric interactions in 1, but not in 2 and 3. Activation parameters for enantiomer interconversion were obtained by DNMR methods in C6D5Cl: Delta H-double dagger = 18.1(1) kcal mol(-1), Delta S-double dagger= -0.6(1) cal mol(-1) K-1 for Ar = Ph (1a) and Delta H-double dagger = 18.6(4) kcal mol(-1), Delta S-double dagger = 5.2(6) cal mol(-1) K-1 for Ar = 2-anisyl (1b). DFT computational investigation of the origin of the interconversion barrier on model compounds revealed steric destabilization of the inversion TS. (C) 2017 Elsevier Ltd. All rights reserved.

引用

页码：3823 / 3830

页数：8

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