Journal of the American Chemical Society p. 8729 - 8737 (2014)
Update date:2022-07-30
Topics:
Kumarasamy, Elango
Raghunathan, Ramya
Jockusch, Steffen
Ugrinov, Angel
Sivaguru
Atropisomeric maleimides were synthesized and employed for stereospecific [2 + 2] photocycloaddition. Efficient reaction was observed under direct irradiation, triplet-sensitized UV irradiation, and non-metal catalyzed visible-light irradiation, leading to two regioisomeric (exo/endo) photoproducts with complete chemoselectivity (exclusive [2 + 2] photoproduct). High enantioselectivity (ee > 98%) and diastereoselectivity (dr > 99:1%) were observed under the employed reaction conditions and were largely dependent on the substituent on the maleimide double bond but minimally affected by the substituents on the alkenyl tether. On the basis of detailed photophysical studies, the triplet energies of the maleimides were estimated. The triplet lifetimes appeared to be relatively short at room temperature as a result of fast [2 + 2] photocycloaddition. For the visible-light mediated reaction, triplet energy transfer occurred with a rate constant close to the diffusion-limited value. The mechanism was established by generation of singlet oxygen from the excited maleimides. The high selectivity in the photoproduct upon reaction from the triplet excited state was rationalized on the basis of conformational factors as well as the type of diradical intermediate that was preferred during the photoreaction.
View MoreChangzhou Qidi Chemical Co., Ltd
website:http://www.czqdhg.com/
Contact:86-519-83382137
Address:128-1-16# HuaYuan Street,Hutang Town,Wujin District,Changzhou City,P.R.China.
Daqing New Century Fine Chemical Co., Ltd.(expird)
Contact:010-57126694
Address:No.39, jinxing cun, honggang district
Beijing Mediking Biopharm Co., Ltd.
Contact:+86-10-89753524/81760121/81769521
Address:Hongxianghong Incubator, Beiqijia Town, Changping district, Beijing, China
Contact:+86-10-67147360/67107388
Address:No.18 Guangming Zhongjie, Chongwen District, Beijing, 100061, China
Shenzhen JYMed Technology Co.,Ltd.
website:http://www.jymedtech.com
Contact:+86-755-26612112
Address:1#8,9/F, Biomedicine innovation Industrial Park, No.14, Jinhui Road, Pingshan Sistrict, Shenzhen, China
Doi:10.1021/ol501459e
(2014)Doi:10.1016/j.tetlet.2014.05.009
(2014)Doi:10.1016/j.ejmech.2014.05.010
(2014)Doi:10.1016/0039-128X(94)90101-5
(1994)Doi:10.1021/ja00097a020
(1994)Doi:10.1016/0277-5387(94)00231-3
(1995)