Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization

Andrew J. Clark; Alana E. C. Collis; David J. Fox; Lauren L. Halliwell; Natalie James; Rachel K. O'Reilly; Hemal Parekh; Andrew Ross; Andrew B. Sellars; Helen Willcock; Paul Wilson

doi:10.1021/jo301429a

Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization

Andrew J. Clark, Alana E. C. Collis, David J. Fox, Lauren L. Halliwell, Natalie James, Rachel K. O'Reilly, Hemal Parekh, Andrew Ross, Andrew B. Sellars, Helen Willcock, Paul Wilson

Chemistry

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a–e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4·5H2O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal “activators generated by electron transfer” (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4·5H2O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical–polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4·5H2O and Bu4NBH4.

Original language	English
Pages (from-to)	6778-6788
Journal	Journal of Organic Chemistry
Volume	77
Issue number	16
DOIs	https://doi.org/10.1021/jo301429a
Publication status	Published - 6 Aug 2012

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Clark, A. J., Collis, A. E. C., Fox, D. J., Halliwell, L. L., James, N., O'Reilly, R. K., Parekh, H., Ross, A., Sellars, A. B., Willcock, H., & Wilson, P. (2012). Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization. Journal of Organic Chemistry, 77(16), 6778-6788. https://doi.org/10.1021/jo301429a

@article{4763a69d79bf42478a006e2e6464b378,

title = "Atom-Transfer Cyclization with CuSO4/KBH4: A Formal {"}Activators Generated by Electron Transfer{"} Process Also Applicable to Atom-Transfer Polymerization",

abstract = "The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a–e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4·5H2O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal “activators generated by electron transfer” (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4·5H2O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical–polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4·5H2O and Bu4NBH4.",

author = "Clark, {Andrew J.} and Collis, {Alana E. C.} and Fox, {David J.} and Halliwell, {Lauren L.} and Natalie James and O'Reilly, {Rachel K.} and Hemal Parekh and Andrew Ross and Sellars, {Andrew B.} and Helen Willcock and Paul Wilson",

year = "2012",

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doi = "10.1021/jo301429a",

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Clark, AJ, Collis, AEC, Fox, DJ, Halliwell, LL, James, N, O'Reilly, RK, Parekh, H, Ross, A, Sellars, AB, Willcock, H & Wilson, P 2012, 'Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization', Journal of Organic Chemistry, vol. 77, no. 16, pp. 6778-6788. https://doi.org/10.1021/jo301429a

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T1 - Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization

AU - Clark, Andrew J.

AU - Collis, Alana E. C.

AU - Fox, David J.

AU - Halliwell, Lauren L.

AU - James, Natalie

AU - O'Reilly, Rachel K.

AU - Parekh, Hemal

AU - Ross, Andrew

AU - Sellars, Andrew B.

AU - Willcock, Helen

AU - Wilson, Paul

PY - 2012/8/6

Y1 - 2012/8/6

N2 - The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a–e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4·5H2O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal “activators generated by electron transfer” (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4·5H2O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical–polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4·5H2O and Bu4NBH4.

AB - The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a–e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO4·5H2O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal “activators generated by electron transfer” (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO4·5H2O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical–polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO4·5H2O and Bu4NBH4.

UR - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000307526700008&KeyUID=WOS:000307526700008

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DO - 10.1021/jo301429a

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SP - 6778

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 16

ER -

Atom-Transfer Cyclization with CuSO4/KBH4: A Formal "Activators Generated by Electron Transfer" Process Also Applicable to Atom-Transfer Polymerization

Abstract

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