Synthesis of Dihydrobenzooxaphospholes via Cyclocondensation of 2-Phosphinylphenol and Aldehydes

doi:10.6023/cjoc202202012

Abstract

A facile method to synthesize dihydrobenzooxaphospholes was developed from a p-toluenesulfonic acid (p-TSA)- promoted intermolecular cyclocondensation of the readily available 2-phosphinylphenol and aromatic aldehydes. The desired products were obtained as a mixture of stereoisomers. Interestingly, the diastereoisomers could be separated easily by flash column chromatography. The gram-scale and diastereoselective syntheses were also successfully performed.

Key words: organophosphorus, dihydrobenzooxaphosphole, cyclocondensation, diastereoselectivity

Cite this article

Xueli Zhu, Shaoli Yang, Caixia Jia, Jing Li, Zheng Duan. Synthesis of Dihydrobenzooxaphospholes via Cyclocondensation of 2-Phosphinylphenol and Aldehydes[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2201-2213.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

Scheme 1. Intramolecular cyclization to dihydro-oxaphosphole

Scheme 2. Synthesis of 2-phosphinylphenol

Entry	Acid	Solvent	Temp./℃	Time/h	Yield^b/%
1	p-TSA (2.0 equiv.)	Toluene	120	12	45+33
2	p-TSA (2.0 equiv.)	MeCN	120	12	Trace
3	p-TSA (2.0 equiv.)	1,2-Dichloroethane	120	12	48+39
4	p-TSA (2.0 equiv.)	1,2-Dichloroethane	100	12	12+Trace
5	p-TSA (2.0 equiv.)	1,2-Dichloroethane	80	12	Trace
6	p-TSA (1.0 equiv.)	1,2-Dichloroethane	120	12	9+Trace
7	p-TSA (10 mol%)	1,2-Dichloroethane	120	12	Trace
8	p-TSA (2.0 equiv.)	1,2-Dichloroethane	120	8	41+29
9	CF₃COOH (2.0 equiv.)	1,2-Dichloroethane	120	12	56+27

Table 1. Optimization of the reaction conditionsa

Table 2. Reaction scope of 4 and 5a

Scheme 3. Gram-scale reaction with 4n

Figure 1. X-ray crystal structures of trans-6o (A, CCDC: 2130832) and cis-6o (B, CCDC: 2088691) All hydrogen atoms have been omitted for the sake of clarity, and the level set for thermal ellipsoids of all atoms is 30%. Main bond lengths (nm) and angles (°): trans-6o: P(1)—C(1) 0.1792(2), P(1)—O(1) 0.14807(15), P(1)—C(13) 0.1868(2), P(1)—C(14) 0.1784(2), O(2)— C(13) 0.1452(3), O(2)—C(15) 0.1374(3), C(12)—C(13) 0.1497(3), C(14)—C(15) 0.1383(3), O(1)—P(1)—C(1) 11.240(9), O(1)—P(1)— C(13) 11.698(10), O(1)—P(1)—C(14) 11.780(10), O(2)—C(13)—P(1) 10.663(15), C(12)—C(13)—P(1) 11.524(15), C(13)—P(1)—C(14) 9.057(10), C(13)—O(2)—C(15) 11.196(17). cis-6o: P(1)—C(1) 0.1796(2), P(1)—O(1) 0.14753(18), P(1)—C(13) 0.1866(3), P(1)—C(13) 0.1866(3), O(2)—C(13) 0.1444(3), O(2)—C(14) 0.1374(3), C(12)— C(13) 0.1505(3), C(14)—C(15) 0.1379(3), O(1)—P(1)—C(1) 11.248(12), O(1)—P(1)—C(13) 11.430(12), O(1)—P(1)—C(15) 11.852(11), C(1)— P(1)—C(13) 11.004(11), C(1)—P(1)—C(15) 10.874(11), C(13)—P(1)— C(13) 9.078(12), C(14)—O(2)—C(13) 11.31(2)

Entry	Acid	Yield^b/%
1	(rac)-BINOL-phosphoric acid (2.0 equiv.)	79
2	(R)-BINOL-phosphoric acid (2.0 equiv.)	76
2	(S)-BINOL-phosphoric acid (2.0 equiv.)	62

Table 3. BINOL-phosphoric acids promoted reactionsa

References 18

[1]	Tang, W.; Qu, B.; Capacci, A. G.; Rodriguez, S.; Wei, X.; Haddad, N.; Narayanan, B.; Ma, S.; Grinberg, N.; Yee, N. K.; Krishnamurthy, D.; Senanayake, C. H. Org. Lett. 2010, 12, 176. doi: 10.1021/ol9025815
[2]	(a) Qu, B.; Samankumara, L. P.; Ma, S.; Fandrick, K. R.; Desrosiers, J.-N.; Rodriguez, S.; Li, Z.; Haddad, N.; Han, Z. S.; McKellop, K.; Pennino, S.; Grinberg, N.; Gonnella, N. C.; Song, J. J.; Senanayake, C. H. Angew. Chem., Int. Ed. 2014, 53, 14428. doi: 10.1002/anie.201408929 pmid: 29896393
	(b) Rodriguez, S.; Qu, B.; Fandrick, K. R.; Buono, F.; Haddad, N.; Xu, Y.; Herbage, M. A.; Zeng, X.; Ma, S.; Grinberg, N.; Lee, H.; Han, Z. S.; Yee, N. K.; Senanayake, C. H. Adv. Synth. Catal. 2014, 356, 301. doi: 10.1002/adsc.201300727 pmid: 29896393
	(c) Qu, B.; Mangunuru, H. P. R.; Wei, X.; Fandrick, K. R.; Desrosiers, J.-N.; Sieber, J. D.; Kurouski, D.; Haddad, N.; Samankumara, L. P.; Lee, H.; Savoie, J.; Ma, S.; Grinberg, N.; Sarvestani, M.; Yee, N. K.; Song, J. J.; Senanayake, C. H. Org. Lett. 2016, 18, 4920. doi: 10.1021/acs.orglett.6b02401 pmid: 29896393
	(d) Handa, S.; Andersson, M. P.; Gallou, F.; Reilly, J.; Lipshutz, B. Angew. Chem., Int. Ed. 2016, 55, 4914. doi: 10.1002/anie.201510570 pmid: 29896393
	(e) Qu, B.; Haddad, N.; Rodriguez, S.; Sieber, J. D.; Desrosiers, J.-N.; Patel, N. D.; Zhang, Y.; Grinberg, N.; Lee, H.; Ma, S.; Ries, U. J.; Yee, N. K.; Senanayake, C. H. J. Org. Chem. 2016, 81, 745. doi: 10.1021/acs.joc.5b02368 pmid: 29896393
	(f) Wei, X.; Qu, B.; Zeng, X.; Savoie, J.; Fandrick, K. R.; Desrosiers, J.-N.; Tcyrulnikov, S.; Marsini, M. A.; Buono, F.; Li, Z.; Yang, B.-S.; Tang, W.; Haddad, N.; Gutierrez, O.; Wang, J.; Lee, H.; Ma, S.; Campbell, S.; Lorenz, J. C.; Eckhardt, M.; Himmelsbach, F.; Peters, S.; Patel, N. D.; Tan, Z.; Yee, N. K.; Song, J. J.; Roschangar, F.; Kozlowski, M. C.; Senanayake, C. H. J. Am. Chem. Soc. 2016, 138, 15473. doi: 10.1021/jacs.6b09764 pmid: 29896393
	(g) Haddad, N.; Mangunuru, H. P. R.; Fandrick, K. R.; Qu, B.; Sieber, J. D.; Rodriguez, S.; Desrosiers, J.-N.; Patel, N. D.; Lee, H.; Kurouski, D.; Grinberg, N.; Yee, N. K.; Song, J. J.; Senanayake, C. H. Adv. Synth. Catal. 2016, 358, 3522. doi: 10.1002/adsc.201600889 pmid: 29896393
	(h) Li, G.; Wang, X.-J.; Zhang, Y.; Tan, Z.; Decroos, P.; Lorenz, J. C.; Wei, X.; Grinberg, N.; Yee, N. K.; Senanayake, C. H. J. Org. Chem. 2017, 82, 5456. doi: 10.1021/acs.joc.7b00491 pmid: 29896393
	(i) Patel, N. D.; Sieber, J. D.; Tcyrulnikov, S.; Simmons, B. J.; Rivalti, D.; Duvvuri, K.; Zhang, Y.; Gao, D. A.; Fandrick, K. R.; Haddad, N.; Lao, K. S.; Mangunuru, H. P. R.; Biswas, S.; Qu, B.; Grinberg, N.; Pennino, S.; Lee, H.; Song, J. J.; Gupton, B. F.; Garg, N. K.; Kozlowski, M. C.; Senanayake, C. H. ACS Catal. 2018, 8, 10190. doi: 10.1021/acscatal.8b02509 pmid: 29896393
	(j) Zatolochnaya, O. V.; Rodriguez, S.; Zhang, Y.; Lao, K. S.; Tcyrulnikov, S.; Li, G.; Wang, X.-J.; Qu, B.; Biswas, S.; Mangunuru, H. P. R.; Rivalti, D.; Sieber, J. D.; Desrosiers, J.-N.; Leung, J. C.; Grinberg, N.; Lee, H.; Haddad, N.; Yee, N. K.; Song, J. J.; Kozlowski, M. C.; Senanayake, C. H. Chem. Sci. 2018, 9, 4505. doi: 10.1039/c8sc00434j pmid: 29896393
	(k) Lu, Z.; Jasinski, J. B.; Handa, S.; Hammond, G. B. Org. Biomol. Chem. 2018, 16, 2748. doi: 10.1039/C8OB00527C pmid: 29896393
	(l) Li, G.; Zatolochnaya, O. V.; Wang, X.-J.; Rodriguez, S.; Qu, B.; Desrosiers, J.-N.; Mangunuru, H. P. R.; Biswas, S.; Rivalti, D.; Karyakarte, S. D.; Sieber, J. D.; Grinberg, N.; Wu, L.; Lee, H.; Haddad, N.; Fandrick, D. R.; Yee, N. K.; Song, J. J.; Senanayake, C. H. Org. Lett. 2018, 20, 1725. doi: 10.1021/acs.orglett.8b00139 pmid: 29896393
	(m) Xu, G.; Senanayake, C. H.; Tang, W. Acc. Chem. Res. 2019, 52, 1101. doi: 10.1021/acs.accounts.9b00029 pmid: 29896393
[3]	Zhu, J.; Huang, L.; Dong, W.; Li, N.; Yu, X.; Deng, W.-P.; Tang, W. Angew. Chem., Int. Ed. 2019, 58, 16119. doi: 10.1002/anie.201910008
[4]	Li, C.; Wan, F.; Chen, Y.; Peng, H.; Tang, W.; Yu, S.; McWilliams, J. C.; Mustakis, J.; Samp, L.; Maguire, R. J. Angew. Chem., Int. Ed. 2019, 58, 13573. doi: 10.1002/anie.201908089
[5]	Dong, W.; Xu, X.; Ma, H.; Lei, Y.; Lin, Z.; Zhao, W. J. Am. Chem. Soc. 2021, 143, 10902. doi: 10.1021/jacs.1c06697
[6]	Qian, C.; Tang, W. Org. Lett. 2020, 22, 4483. doi: 10.1021/acs.orglett.0c01490
[7]	Xiong, W.; Xu, G.; Yu, X.; Tang, W. Organometallics 2019, 38, 4003. doi: 10.1021/acs.organomet.9b00194
[8]	(a) Takale, B. S.; Thakore, R. R.; Handa, S.; Gallou, F.; Reilly, J.; Lipshutz, B. H. Chem. Sci. 2019, 10, 8825. doi: 10.1039/C9SC02528F
	(b) Sieber, J. D.; Buono, F.; Brusoe, A.; Desrosiers, J. N.; Haddad, N.; Lorenz, J. C.; Xu, Y.; Wu, H.; Zhang, L.; Han, Z. S. Roschangar, F.; Song, J. J.; Yee, N. K.; Senanayake, C. H. J. Org. Chem. 2019, 84, 4926. doi: 10.1021/acs.joc.8b03040
[9]	Yang, H.; Sun, J.; Gu, W.; Tang, W. J. Am. Chem. Soc. 2020, 142, 8036. doi: 10.1021/jacs.0c02686 pmid: 32240585
[10]	Li, B.; Li, T.; Aliyu, M.; Li, Z. H.; Tang, W. Angew. Chem., Int. Ed. 2019, 58, 11355. doi: 10.1002/anie.201905174
[11]	Wu, T.; Kang, X.; Bai, H.; Xiong, W.; Xu, G.; Tang, W. Org. Lett. 2020, 22, 4602. doi: 10.1021/acs.orglett.0c01129
[12]	Heinicke, J.; Tzschach, A. Phosphorus Sulfur Relat. Elem. 1985, 25, 345.
[13]	(a) Li, S.; Han, Z. S.; Viereck, P.; Lee, H.; Kurouski, D.; Senanayake, C. H.; Tsantrizos, Y. S. Org. Lett. 2017, 19, 894. doi: 10.1021/acs.orglett.7b00051
	(b) Han, Z.S.; Wu, H.; Xu, Y.; Zhang, Y.; Qu, B.; Li, Z.; Caldwell, D. R.; Fandrick, K. R.; Zhang, L.; Roschangar, F.; Song, J.; Senanayake, C. H. Org. Lett. 2017, 19, 1796. doi: 10.1021/acs.orglett.7b00568
[14]	(a) Heinicke, J.; Tzschach, A. Z. Chem 1980, 20, 342. doi: 10.1002/zfch.19800200912 pmid: 22899483
	(b) Washington, M. P.; Gudimetla, V. B.; Laughlin, F. L.; Deligonul, N.; He, S.; Payton, J. L.; Simpson, M. C.; Protasiewicz, J. D. J. Am. Chem. Soc. 2010, 132, 4566. doi: 10.1021/ja1009426 pmid: 22899483
	(c) Washington, M. P.; Payton, J. L.; Simpson, M. C.; Protasiewicz, J. D. Organometallics 2011, 30, 1975. doi: 10.1021/om200014f pmid: 22899483
	(d) Laughlin, F. Li; Deligonul, N.; Rheingold, A. L.; Golen, J. A.; Laughlin, B. J.; Smith, R. C.; Protasiewicz, J. D. Organometallics 2013, 32, 7116. doi: 10.1021/om400838g pmid: 22899483
	(e) Wu, S. S.; Rheingold, A. L.; Protasiewicz, J. D. Chem. Commun. 2014, 50, 11036. doi: 10.1039/C4CC05259E pmid: 22899483
	(f) Laughlin, F. L.; Rheingold, A. L.; Deligonul, N.; Laughlin, B. J.; Smith, R. C.; Higham, L. J.; Protasiewicz, J. D. Dalton Trans. 2012, 41, 12016. pmid: 22899483
	(g) Wu, S. S.; Deligonal, N.; Protasiewicz, J. D. Dalton Trans. 2013, 42, 14866. doi: 10.1039/c3dt51919h pmid: 22899483
[15]	Oehme, H.; Leissring, E. Tetrahedron 1981, 37, 753. doi: 10.1016/S0040-4020(01)97693-8
[16]	Huang, H.; Denne, J.; Yang, C.-H.; Wang, H.; Kang, J. Y. Angew. Chem., Int. Ed. 2018, 57, 6624. doi: 10.1002/anie.201802082
[17]	(a) Melvin, L. S. Tetrahedron Lett. 1981, 22, 3375. doi: 10.1016/S0040-4039(01)81909-2 pmid: 29924885
	(b) Heinicke, J.; Böhle, I.; Tzschach, A. J. Organomet. Chem. 1986, 317, 11. doi: 10.1016/S0022-328X(00)99340-9 pmid: 29924885
	(c) Dhawan, B.; Redmore, D. J. Org. Chem. 1991, 56, 833. doi: 10.1021/jo00002a060 pmid: 29924885
	(d) Li, S. S.; Wang, G. Q. Phosphorus Sulfur Relat. Elem. 1991, 61, 119. doi: 10.1080/10426509108027344 pmid: 29924885
	(e) Paladino, J.; Guyard, C.; Thurieau, C.; Fauchère, J. - L. Helv. Chim. Acta 1993, 76, 2465. doi: 10.1002/hlca.19930760706 pmid: 29924885
	(f) Taylor, C. M.; Watson, A. J. Curr. Org. Chem. 2004, 8, 623. doi: 10.2174/1385272043370717 pmid: 29924885
	(g) Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem., Int. Ed. 2004, 43, 2206. doi: 10.1002/anie.200300590 pmid: 29924885
	(h) Jayasundera, K. P.; Watson, A. J.; Taylor, C. M. Tetrahedron Lett. 2005, 46, 4311. doi: 10.1016/j.tetlet.2005.04.104 pmid: 29924885
	(i) Yilmaz, E.; Bier, D.; Guillory, X.; Briels, J.; Ruiz-Blanco, Y. B.; Sanchez-Garcia, E.; Ottmann, C.; Kaiser, M. Chem.-Eur. J. 2018, 24, 13807. doi: 10.1002/chem.201801074 pmid: 29924885
	(j) Korb, M.; Lang, H. Chem. Soc. Rev. 2019, 48, 2829. doi: 10.1039/C8CS00830B pmid: 29924885
	(k) Patel, J. J.; Blackburn, T.; Alessi, M.; Sawinski, H.; Snieckus, V. Org. Lett. 2020, 22, 3860. doi: 10.1021/acs.orglett.0c01123 pmid: 29924885
[18]	(a) Kenny, N. P.; Rajendran, K. V.; Gilheany, D. G. Chem. Commun. 2015, 51, 16561. doi: 10.1039/C5CC06389B
	(b) Huang, H.; Denne, J.; Yang, C. H.; Wang, H.; Kang, J. Y. Angew. Chem., Int. Ed. 2018, 57, 6624. doi: 10.1002/anie.201802082
	(c) Melvin, L. S. Tetrahedron Lett. 1981, 22, 3375. doi: 10.1016/S0040-4039(01)81909-2
	(d) Yang, S. X.; Li, Y. G.; Wang, J. Chin. J. Org. Chem. 1984, 4, 271. (in Chinese)
	( 杨石先, 李玉桂, 王坚, 有机化学, 1984, 4, 271.)

通过邻羟基苯基膦和醛的缩合反应合成苯并氧杂磷杂环戊烯