SET or TET? Iron-catalyzed aminocarbonylation of unactivated alkyl halides with amines, amides, and indoles via a substrate dependent mechanism

doi:10.1016/S1872-2067(22)64208-6

Abstract

Abstract:

Iron-catalyzed carbonylation reactions are highly desirable in our sustainability-advocating chemical community because of its low cost, abundance, and potential for distinct and complementary reactivity patterns. Meanwhile, alkyl bromides as well as low nucleophilic amides and indoles are considered to be particularly challenge substrates for carbonylation reactions. Herein, we report an iron-catalyzed carbonylative coupling of unactivated alkyl halides with amines, amides, and indoles to assemble amide structural units, affording various amides, imides and N-acyl indoles with excellent yields and unprecedented functional group compatibility. Remarkably, our approach also represents the example on Fe-catalyzed aminocarbonylation of alkyl halides. Our preliminary mechanistic studies suggest that the reaction pathway is substrate dependent: the carbonylation proceeds via a radical pathway when alkyl iodides were used; while a two-electron transfer (TET) process occurred when alkyl bromides served as the electrophiles.

Key words: Iron catalysis, Carbonylative coupling, Alkyl halides, Amides, Imides

Han-Jun Ai, Fengqian Zhao, Xiao-Feng Wu. SET or TET? Iron-catalyzed aminocarbonylation of unactivated alkyl halides with amines, amides, and indoles via a substrate dependent mechanism[J]. Chinese Journal of Catalysis, 2023, 47: 121-128.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64208-6

https://www.cjcatal.com/EN/Y2023/V47/I4/121

Figures/Tables 7

Fig. 1. Representative bioactive amides and imides and transition-metal-catalyzed aminocarbonylation of halocarbons.

Table 1 Optimization of the reaction conditions.a

Entry	Deviation from standard condition	Yield ^b (%)
1	none	94^c
2	No 1,10-Phen	85
3	Bpy instead of 1,10-Phen	84
4	PPh₃ instead of 1,10-Phen	62
5	DPPP instead of 1,10-Phen	26
6	PhDavePhos instead of 1,10-Phen	92
7	using Fe(CO)₃(cot) or Fe₃(CO)₁₂ as catalyst	17 or 89
8	using FeBr₂, FeF₃, or Fe(OTf)₃ as catalyst	0
9	PhMe instead of Bu₂O	87
10	DMSO instead of Bu₂O	0
11	using KO^tBu as base	10<
12	using DBU or Et₃N as base	0

Fig. 2. Scope of the anilines and alkyl bromides. a Unless otherwise noted, reactions were run at a 0.2 mmol scale under the standard conditions. Isolated yields are reported. b 2 equivalents of alkyl bromides and Cs2CO3 were used. c 1 mL of Bu2O was used due to the poor solubility. d 0.6 mL of Bu2O was used due to the poor solubility. Bpin = pinacol borate group. PMP = para-methoxyphenyl.

Fig. 3. Scope of other electrophiles. a Unless otherwise noted, reactions were run at a 0.2 mmol scale under the standard conditions. Isolated yields are reported. b Yield was determined by GC. c Yield was determined by NMR. Quant. = quantitative yield.

Fig. 4. Scope of other nucleophiles. The reactions were run at a 0.2 mmol scale under the standard conditions. Isolated yields are reported. Quant. = quantitative yield.

Fig. 5. Mechanistic studies.

Fig. 6. Proposed mechanism.

References

[1]	A. Greenberg, C. M. Breneman, J. F. Liebman, The amide linkage: Structural Significance in Chemistry, Biochemistry, and Materials Science, Wiley, New York, 2000.
[2]	J. W. Clader, J. Med. Chem., 2004, 47, 1-9.
[3]	L. Crespo, G. Sanclimens, M. Pons, E. Giralt, M. Royo, F. Albericio, Chem. Rev., 2005, 105, 1663-1682.
[4]	U. Boas, J. Brask, K. J. Jensen, Chem. Rev., 2009, 109, 2092-2118.
[5]	X. Guo, A. Facchetti, T. J. Marks, Chem. Rev., 2014, 114, 8943-9021.
[6]	I. Ziccarelli, R. Mancuso, F. Giacalone, C. Calabrese, V. La Parola, A. De Salvo, N. Della Ca’, M. Gruttadauria, B. Gabriele, J. Catal., 2022, 413, 1098-1110.
[7]	G. Kiss, Chem. Rev., 2001, 101, 3435-3456.
[8]	B. Gabriele, Carbon Monoxide in Organic Synthesis: Carbonylation Chemistry, Wiley-VCH, Weinheim, 2021.
[9]	L.-J. Cheng, N. P. Mankad, Chem. Soc. Rev., 2020, 49, 8036-8064.
[10]	S. Sumino, A. Fusano, T. Fukuyama, I. Ryu, Acc. Chem. Res., 2014, 47, 1563-1574.
[11]	J.-B. Peng, F.-P. Wu, X.-F. Wu, Chem. Rev., 2019, 119, 2090-2127.
[12]	R. J. Atkins, A. Banks, R. K. Bellingham, G. F. Breen, J. S. Carey, S. K. Etridge, J. F. Hayes, N. Hussain, D. O. Morgan, P. Oxley, S. C. Passey, T. C. Walsgrove, A. S. Wells, Org. Process Res. Dev., 2003, 7, 663-675.
[13]	C. F. J. Barnard, Organometallics, 2008, 27, 5402-5422.
[14]	L.-J. Cheng, N. P. Mankad, Acc. Chem. Res., 2021, 54, 2261-2274.
[15]	L. Wu, X. Fang, Q. Liu, R. Jackstell, M. Beller, X.-F. Wu, ACS Catal., 2014, 4, 2977-2989.
[16]	I. Ryu, K. Nagahara, N. Kambe, N. Sonoda, S. Kreimerman, M. Komatsu, Chem. Commun., 1998, 1953-1954.
[17]	O. Itsenko, T. Kihlberg, B. Långström, J. Org. Chem., 2004, 69, 4356-4360.
[18]	T. Fukuyama, S. Nishitani, T. Inouye, K. Morimoto, I. Ryu, Org. Lett., 2006, 8, 1383-1386.
[19]	T. Fukuyama, T. Inouye, I. Ryu, J. Organomet. Chem., 2007, 692, 685-690.
[20]	S. Y. Chow, M. Y. Stevens, L. Åckerbladh, S. Bergman, L. R. Odell, Chem. Eur. J., 2016, 22, 9155-9161.
[21]	O. Rahman, B. Långström, C. Halldin, ChemistrySelect, 2016, 1, 2498-2501.
[22]	M. Sardana, J. Bergman, C. Ericsson, L. P. Kingston, M. Schou, C. Dugave, D. Audisio, C. S. Elmore, J. Org. Chem., 2019, 84, 16076-16085.
[23]	B. T. Sargent, E. J. Alexanian, Angew. Chem. Int. Ed., 2019, 58, 9533-9536.
[24]	G. M. Torres, Y. Liu, B. A. Arndtsen, Science, 2020, 368, 318-323.
[25]	F. Zhao, H.-J. Ai, X.-F. Wu, Angew. Chem.Int. Ed., 2022, 61, e202200062.
[26]	J. Hartwig, Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books, Sausalito, 2010.
[27]	A. C. Bissember, A. Levina, G. C. Fu, J. Am. Chem. Soc., 2012, 134, 14232-14237.
[28]	M. R. Kwiatkowski, E. J. Alexanian, Acc. Chem. Res., 2019, 52, 1134-1144.
[29]	R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev., 2011, 111, 1417-1492.
[30]	B. T. Sargent, E. J. Alexanian, J. Am. Chem. Soc., 2016, 138, 7520-7523.
[31]	L.-J. Cheng, S. M. Islam, N. P. Mankad, J. Am. Chem. Soc., 2018, 140, 1159-1164.
[32]	L.-J. Cheng, N. P. Mankad, J. Am. Chem. Soc., 2020, 142, 80-84.
[33]	Q. Liu, H. Zhang, A. Lei, Angew. Chem. Int. Ed., 2011, 50, 10788-10799.
[34]	Y. Liu, Y.-H. Chen, H. Yi, A. Lei, ACS Catal., 2022, 12, 7470-7485.
[35]	B. Lu, M. Xu, X. Qi, M. Jiang, W.-J. Xiao, J.-R. Chen, J. Am. Chem. Soc., 2022, 144, 14923-14935.
[36]	M. P. Cooke, J. Am. Chem. Soc., 1970, 92, 6080-6082.
[37]	J. P. Collman, N. W. Hoffman, J. Am. Chem. Soc., 1973, 95, 2689-2691.
[38]	J. P. Collman, S. R. Winter, D. R. Clark, J. Am. Chem. Soc., 1972, 94, 1788-1789.
[39]	J. P. Collman, S. R. Winter, R. G. Komoto, J. Am. Chem. Soc., 1973, 95, 249-250.
[40]	A. Stockis, E. Weissberger, J. Am. Chem. Soc., 1975, 97, 4288-4292.
[41]	M. Periasamy, A. Mukkanti, D. S. Raj, Organometallics, 2004, 23, 6323-6326.
[42]	M. Periasamy, A. Mukkanti, D. S. Raj, Organometallics, 2004, 23, 619-621.
[43]	C. Rameshkumar, M. Periasamy, Synlett, 2000, 1619-1621.
[44]	C. Rameshkumar, M. Periasamy, Organometallics, 2000, 19, 2400-2402.
[45]	M. Periasamy, C. Rameshkumar, U. Rhadhakrishnan, J.-J. Brunet, J. Org. Chem., 1998, 63, 4930-4935.
[46]	K. M. Driller, S. Prateeptongkum, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2011, 50, 537-541.
[47]	S. Prateeptongkum, K. M. Driller, R. Jackstell, M. Beller, Chem. Asian J., 2010, 5, 2173-2176.
[48]	K. M. Driller, H. Klein, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2009, 48, 6041-6044.
[49]	S. Prateeptongkum, K. M. Driller, R. Jackstell, A. Spannenberg, M. Beller, Chem. Eur. J., 2010, 16, 9606-9615.
[50]	M. Pizzetti, A. Russo, E. Petricci, Chem. Eur. J., 2011, 17, 4523-4528.
[51]	T. Susuki, J. Tsuji, J. Org. Chem., 1970, 35, 2982-2986.
[52]	T. N. Allah, S. Savourey, J. C. Berthet, E. Nicolas, T. Cantat, Angew. Chem. Int. Ed., 2019, 58, 10884-10887.
[53]	S. L. Buchwald, C. Bolm, Angew. Chem. Int. Ed., 2009, 48, 5586-5587.
[54]	C. Walling, A. Cioffari, J. Am. Chem. Soc., 1972, 94, 6059-6064.
[55]	In the reaction, Cs₂CO₃ been transformed into CsHCO₃ which will give Cs₂CO₃, H₂O, and CO₂ after thermal disproportionation. The produced H₂O will react with RX to give ROH which then produces RCO₂R after carbonylation reaction. See: H.-J. Ai, H. Wang, C.-L. Li, X.-F. Wu, ACS Catal., 2020, 10, 5147-5152.
[56]	H.-J. Ai, B. N. Leidecker, P. Dam, C. Kubis, J. Rabeah, X.-F. Wu, Angew. Chem. Int. Ed., 2022, 61, e202211939.
[57]	J. Y. Wang, A. E. Strom, J. F. Hartwig. J. Am. Chem. Soc., 2018, 140, 7979-7993.
[58]	J. P. Collman, R. G. Finke, J. N. Cawse, J. I. Brauman, J. Am. Chem. Soc., 1977, 99, 2515-2526.
[59]	J. Guo, H. D. Pham, Y.-B. Wu, D. Zhang, X. Wang, ACS Catal., 2020, 10, 1520-1527.