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...
| Main Authors: | , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2021
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| Online Access: | https://hdl.handle.net/10356/151801 |
| _version_ | 1826124136819195904 |
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| author | Ge, Yicen Cui, Xi-Yang Tan, Siu Min Jiang, Huan Ren, Jingyun Lee, Nicholas Lee, Richmond Tan, Choon-Hong |
| 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 |
| author_sort | Ge, Yicen |
| collection | NTU |
| 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. |
| first_indexed | 2024-10-01T06:15:44Z |
| format | Journal Article |
| id | ntu-10356/151801 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:15:44Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | ntu-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. |
| spellingShingle | 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 |
| title | 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_short | 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 |
| topic | Science::Chemistry Asymmetric Catalysis Borylation |
| url | https://hdl.handle.net/10356/151801 |
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