Transformation of Benzaldehydes to Benzonitriles via Cyanophosphates without One-Carbon Homologation

Abstract

The transformation of benzaldehydes into benzonitriles via cyanophosphates (CPs) with tetrabutylammonium azide (Bu₄N·N₃) was found to afford a range of benzonitriles in modest-to-high yields. As the CN-carbon of benzonitriles arises from the formyl-carbon of benzaldehydes, this is a new type of CP-reaction, distinctly different from the past one-carbon nitrile homologation. In contrast, the reaction of ketone- or aliphatic aldehyde-CPs with Bu₄N·N₃ resulted in mono-deethylaton forming tetrabutylammonium salts.

Key words

cyanophosphate - tetrabutylammonium azide - mono-deethylaton - benzonitrile - tetrabutylammonium salt

Publication History

Received: 14 February 2024

Accepted after revision: 07 March 2024

Accepted Manuscript online:
07 March 2024

Article published online:
20 March 2024

• References

• 1a Harusawa S, Yoneda R, Kurihara T, Hamada Y, Shioiri T. Chem. Pharm. Bull. 1983; 31: 2932
• 1b Harusawa S, Yoneda R, Kurihara T, Hamada Y, Shioiri T. Tetrahedron Lett. 1984; 25: 427
• 2 For DEPC and CPs, see a review: Harusawa S, Shioiri T. Tetrahedron 2016; 72: 8125
• 3a For CPs, see a review: Harusawa S. Chem. Pharm. Bull. 2020; 68: 1
• 3b Yoneda R, Harusawa S, Kurihara T. J. Org. Chem. 1991; 56: 1827
• 3c Kurihara T, Harusawa S, Yoneda R. J. Synth. Org. Chem. Jpn. 1988; 46: 1164
• 4 Matsunaga K, Endo R, Nagasawa K, Kishida A, Takatori K. J. Org. Chem. 2022; 87: 3707
• 5a For the generation of alkylidene carbenes through tetrazole-fragmentation, see a review: Harusawa S, Yoneyama H, Usami Y. Synthesis 2024; in press
• 5b Yoneyama H, Numata M, Uemura K, Usami Y, Harusawa S. J. Org. Chem. 2017; 82: 5538
• 5c Yoneyama H, Hisaka F, Fujisue D, Usami Y, Zhao Z, Harusawa S. Heterocycles 2018; 98: 106
• 5d Yoneyama H, Uemura K, Usami Y, Harusawa S. Tetrahedron 2017; 73: 6109
• 5e Yoneyama H, Uemura K, Usami Y, Harusawa S. Tetrahedron 2018; 74: 2143
• 5f Yoneyama H, Takatsuji K, Ito A, Usami Y, Harusawa S. Tetrahedron 2021; 82: 131914
• 6a Takahashi Y, Askey HE, Cresswell AJ. Tetrabutylammonium Azide. In e-EROS Encyclopedia of Reagents for Organic Synthesis [Online]. Wiley & Sons; New York: Posted January 13, 2013
• 6b Behrouz S. J. Saudi Chem. Soc. 2017; 21: 220
• 7 9a: The [CH₃CH(CH₃)CH₂(C₆H₄)C(CN)(CH₃)OP(O)(OEt)O]^– peak (m/z 310) was indicated in negative mode of FABMS, while the countercation [Bu₄N]⁺ peak (m/z 242) was revealed in the positive mode of EIMS, as respective molecular ion peaks.
• 8 Kurihara T, Hanakawa M, Harusawa S, Yoneda R. Chem. Pharm. Bull. 1986; 34: 4545
• 9 Kurihara T, Santo K, Harusawa S, Yoneda R. Chem. Pharm. Bull. 1987; 35: 4777
• 10 In a correlation with the present study, Yamaguchi and co-workers recently reported that reaction of naphthyl CPs with allyl borates in the presence of palladium catalyst furnished dearomatized unsaturated nitriles, see: Yanagimoto A, Komatsuda M, Muto K, Yamaguchi J. Org. Lett. 2020; 22: 3423
• 11 Kori R, Murakami K, Nishiyama Y, Toma T, Yokoshima S. Chem. Pharm. Bull. 2021; 69: 278
• 12 Laulhé S, Gori SS, Nantz MH. J. Org. Chem. 2012; 77: 9334
• 13 Bhattacharya S, Biswa J. Langmuir 2011; 27: 1581
• 14 Baeza A, Nájera C, Sansano JM. ARKIVOC 2005; (ix): 353
• 15 Kurihara T, Miki M, Santo K, Harusawa S, Yoneda R. Chem. Pharm. Bull. 1986; 34: 4620
• 16 Antonacci G, Ahlburg A, Fristrup P, Norrby P.-O, Madsen R. Eur. J. Org. Chem. 2017; 2017: 4758
• 17 Zhao Y, Mei G, Wang H, Zhang G, Ding C. Synlett 2019; 30: 1484
• 18 Uchida K, Togo H. Tetrahedron 2019; 75: 130550
• 19 Cohen DT, Buchwald SL. Org. Lett. 2015; 17: 202
• 20 Zhang Z, Liebeskind LS. Org. Lett. 2006; 8: 4331
• 21 Rokade BV, Prabhu KR. J. Org. Chem. 2012; 77: 5364
• 22 Zhang X, Sun J, Ding Y, Yu L. Org. Lett. 2015; 17: 5840
• 23 Shi S, Szostak M. Org. Lett. 2017; 19: 3095
• 24 Fang W.-Y, Qin H.-L. J. Org. Chem. 2019; 84: 5803
• 25 Aikawa K, Nakamura Y, Yokota Y, Toya W, Mikami K. Chem. Eur. J. 2015; 21: 96