Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C6F5)3

doi:10.6023/cjoc202007018

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 766-775.DOI: 10.6023/cjoc202007018 Previous Articles Next Articles

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新型取代基炔类分子的合成及其与B(C₆F₅)₃的反应

席鑫¹, 张公平¹, 李建成¹, 黄艳婷¹, 蒋文军¹, 吴鹏¹, 朱红平¹^,^*()

1 厦门大学化学化工学院固体表面物理化学国家重点实验室厦门 361005

收稿日期:2020-07-06 修回日期:2020-08-17 发布日期:2020-09-16
通讯作者: 朱红平
作者简介:
* Corresponding author. E-mail: hpzhu@xmu.edu.cn
基金资助:
国家自然科学基金面上(21972112); 国家自然科学基金面上(21673191)

Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C₆F₅)₃

Xin Xi¹, Gongping Zhang¹, Jiancheng Li¹, Yanting Huang¹, Wenjun Jiang¹, Peng Wu¹, Hongping Zhu¹^,^*()

1 State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Received:2020-07-06 Revised:2020-08-17 Published:2020-09-16
Contact: Hongping Zhu
Supported by:
the General Project of National Natural Science Foundation of China(21972112); the General Project of National Natural Science Foundation of China(21673191)

Five alkyne compounds of varied novel substituents as Mes₂HSiC≡CPh (1, Mes=2,4,6-Me₃C₆H₂), [^tBuC- (NAr)₂]GeC≡CPh (2, Ar=2,6-ⁱPr₂C₆H₃), [PhC(N^tBu)₂]SnC≡CPPh₂ (3), [HC(CMe)₂(NAr)₂]SnC≡CPPh₂, (4) and [HC(C- Me)₂(NAr)₂]ZnC≡CPPh₂ (5) have been synthesized. Compounds 1 and 2 reacted with B(C₆F₅)₃ by the 1,1-carboboration to give compounds (Ph)(Mes₂HSi)C=C(C₆F₅)B(C₆F₅)₂ (6) and {[^tBuC(NAr)₂]Ge}(Ph)C=C(C₆F₅)B(C₆F₅)₂ (7), respectively, where (F₅C₆)₃B/Mes₂HSi group exchange was suggested to occur initially for the former reaction while the (F₅C₆)₃B/ [^tBuC(NAr)₂]Ge exchange was for the latter one. Compound 6 is a acyclic alkene whereas 7 is viewed as a germanaboracyclo- butene owing to a strong Ge^II→B donor-acceptor bonding being a Ge^II/B frustrated Lewis pair (FLP). Compounds 3~5 reacted with B(C₆F₅)₃ to undergo a ligand coordinated metal group/B(C₆F₅)₃ exchange followed by bonding of metal group at PPh₂, resulting in the formation of a novel type of intramolecular zwitterionic alkynes [PhC(N^tBu)₂]SnP(Ph₂)C≡CB(C₆F₅)₃(8), [HC(CMe)₂(NAr)₂]SnP(Ph₂)C≡CB(C₆F₅)₃ (9), and [HC(CMe)₂(NAr)₂]ZnP(Ph₂)C≡CB(C₆F₅)₃ (10), respectively. Compounds 1~10 have been characterized by spectroscopy and elemental analysis, of which 4, 6, 7, and 10 are further authenticated by X-ray crystallography. The mechanisms of these reactions are discussed.

Key words: alkynes of novel substituents, B(C₆F₅)₃, 1,1-carboboration, group exchange reaction, alkenes of novel substituents

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Xin Xi, Gongping Zhang, Jiancheng Li, Yanting Huang, Wenjun Jiang, Peng Wu, Hongping Zhu. Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C₆F₅)₃[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 766-775.

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Fig. & Tab. 11

Scheme 1. Proposed 1,1-carboboration of substituted alkyne compounds

Scheme 2. Synthesis of mestiylhydrosilylalkyne 1

Scheme 3. Synthesis of amidinatogermyl diphenylphosphanylalkyne 2 and amidinatostannyl diphenyphosphanylalkyne 3

Scheme 4. Synthesis of β-diketiminatostannyl diphenylpho- sphanylalkyne 4 and β-diketiminatozinc diphenylphosphanylalkyne 5

. Thermal ellipsoids are at 50% probability and hydrogen atoms are omitted for clarity. (a) Perpendicular to the direction of axis c; (b) perpendicular to the direction of axis b. Selected bond lengths (nm) and angles (°): Sn(1)—C(2) 0.2197(2), C(1)—C(2) 0.1214(3), P(1)—C(1) 0.1763(3), Sn(1)—N(2) 0.21875(19), Sn(1)—N(1) 0.21872(18); C(2)—Sn(1)—N(2) 93.21(8), C(2)—Sn(1)—N(1) 88.49(8), N(1)—Sn(1)—N(2) 85.29(7), C(1)—C(2)—Sn(1) 166.7(2), P(1)—C(1)—C(2) 171.8(2)

Scheme 5. Reaction of compound 1 with B(C6F5)3 to give product 6

. Thermal ellipsoids are at 50% probability and hydrogen atoms except for that of the SiH are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—C(1) 0.19082(18), B(1)—C(2) 0.1576(3), Si(1)—H(1) 0.1387(18), C(1)—C(2) 0.1361(3); C(2)—C(1)—Si(1) 129.06(15), C(1)—C(2)—B(1) 122.56(17)

Scheme 6. Reaction of 2 with B(C6F5)3 to 7

. Thermal ellipsoids are at 50% probability and hydrogen atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Ge(1)—C(2) 0.19526(15), Ge(1)—B(1) 0.21693(17), Ge(1)—N(1) 0.19705(13), Ge(1)—N(2) 0.19603(12), C(2)—C(1) 0.1362(2), B(1)—C(1) 0.1650(2); Ge(1)—C(2)—C(1) 92.47(10), C(2)—C(1)—B(1) 113.38(13), C(1)—B(1)—Ge(1) 77.63(9), B(1)—Ge(1)—C(2) 75.25(6), N(1)—Ge(1)—N(2) 66.91(5)

Scheme 7. Reactions of 3~5 with B(C6F5)3 to give 8~9, respectively

. Thermal ellipsoids are at 50% probability and hydrogen atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Zn(1)—P(1) 0.23224(4), Zn(1)—N(1) 0.19141(11), Zn(1)—N(2) 0.19177(11), B(1)—C(1) 0.1604(2), P(1)—C(2) 0.17341(14), C(1)—C(2) 0.1211(2); P(1)—Zn(1)—N(2) 129.44(4), P(1)—Zn(1)—N(1) 127.05(4), N(1)—Zn(1)—N(2) 103.22(5), Zn(1)—P(1)—C(2) 109.74(5), Zn(1)—P(1)—C(3) 113.65(5), Zn(1)—P(1)—C(9) 113.93(4), P(1)—C(2)—C(1) 173.05(12), B(1)— C(1)—C(2) 172.68(14)

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新型取代基炔类分子的合成及其与B(C₆F₅)₃的反应

Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C₆F₅)₃

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新型取代基炔类分子的合成及其与B(C6F5)3的反应