Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates
An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine-copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee), and could be further transformed in...
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sg-ntu-dr.10356-1518012021-07-16T05:36:15Z Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates Ge, Yicen Cui, Xi-Yang Tan, Siu Min Jiang, Huan Ren, Jingyun Lee, Nicholas Lee, Richmond Tan, Choon-Hong School of Physical and Mathematical Sciences Science::Chemistry Asymmetric Catalysis Borylation An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine-copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee), and could be further transformed into diverse functionalized allylic compounds without erosion of optical purity. Experimental and DFT mechanistic studies support an SN 2' borylation process catalyzed by a monodentate guanidine-copper(I) complex that proceeds through a special direct enantioconvergent transformation mechanism. Ministry of Education (MOE) Nanyang Technological University We are grateful to Nanyang Technological University (M4011633), the Ministry of Education Tier 2 Grant (MOE2016-T2-1-087), and Singapore University of Technology and Design (T1MOE1706 and IDG31800104) for financial support. Computational resources provided by the National Supercomputing Centre (Singapore) are also gratefully acknowledged. 2021-07-16T05:36:14Z 2021-07-16T05:36:14Z 2019 Journal Article Ge, Y., Cui, X., Tan, S. M., Jiang, H., Ren, J., Lee, N., Lee, R. & Tan, C. (2019). Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates. Angewandte Chemie International Edition, 58(8), 2382-2386. https://dx.doi.org/10.1002/anie.201813490 1433-7851 0000-0003-3190-7855 https://hdl.handle.net/10356/151801 10.1002/anie.201813490 30615241 2-s2.0-85060660939 8 58 2382 2386 en M4011633 MOE2016-T2-1-087 Angewandte Chemie International Edition © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. All rights reserved. |
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Science::Chemistry Asymmetric Catalysis Borylation Ge, Yicen Cui, Xi-Yang Tan, Siu Min Jiang, Huan Ren, Jingyun Lee, Nicholas Lee, Richmond Tan, Choon-Hong Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| description |
An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine-copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee), and could be further transformed into diverse functionalized allylic compounds without erosion of optical purity. Experimental and DFT mechanistic studies support an SN 2' borylation process catalyzed by a monodentate guanidine-copper(I) complex that proceeds through a special direct enantioconvergent transformation mechanism. |
| author2 |
School of Physical and Mathematical Sciences |
| author_facet |
School of Physical and Mathematical Sciences Ge, Yicen Cui, Xi-Yang Tan, Siu Min Jiang, Huan Ren, Jingyun Lee, Nicholas Lee, Richmond Tan, Choon-Hong |
| format |
Article |
| author |
Ge, Yicen Cui, Xi-Yang Tan, Siu Min Jiang, Huan Ren, Jingyun Lee, Nicholas Lee, Richmond Tan, Choon-Hong |
| author_sort |
Ge, Yicen |
| title |
Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| title_short |
Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| title_full |
Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| title_fullStr |
Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| title_full_unstemmed |
Guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| title_sort |
guanidine-copper complex catalyzed allylic borylation for the enantioconvergent synthesis of tertiary cyclic allylboronates |
| publishDate |
2021 |
| url |
https://hdl.handle.net/10356/151801 |
| _version_ |
1707050431037833216 |