87156-76-1Relevant academic research and scientific papers
Water-Promoted Dehydrative Tsuji–Trost Reaction of Non-Derivatized Allylic Alcohols with Sulfinic Acids
Yu, Jing,Chang, Xueping,Ma, Ruitian,Zhou, Qiuju,Wei, Mengmeng,Cao, Xinhua,Ma, Xiantao
supporting information, p. 7238 - 7242 (2020/10/30)
A mild, green and extra activator-free synthesis of allylic sulfones from non-derivatized allylic alcohols and sulfinic acids was developed and only the easily-available Pd(PPh3)4 was used as the catalyst. This new method could be easily scaled up to gram scale, affording the target allylic sulfones in a nearly quantitative yield with water as the sole by-product. Mechanism studies both by various NMR techniques and by theoretical calculations suggested two reaction pathways may be involved in the reaction, which are dependent on the reaction media, that is, an eight-membered ring binding species may be formed in aqueous media between allylic alcohol, sulfinic acid and water, while a six-membered ring binding species may be formed in common aprotic organic solvent between allylic alcohol and sulfinic acid. Both binding species may be accounted for the efficient activation of allylic alcohols via hydrogen bonding.
Reciprocal-Activation Strategy for Allylic Sulfination with Unactivated Allylic Alcohols
Xie, Peizhong,Sun, Zuolian,Li, Shuangshuang,Cai, Xinying,Qiu, Ju,Fu, Weishan,Gao, Cuiqing,Wu, Shisheng,Yang, Xiaobo,Loh, Teck-Peng,Loh, Teck-Peng
supporting information, p. 4893 - 4897 (2020/06/24)
A reciprocal-activation strategy for allylic sulfination with unactivated allylic alcohols was developed. In this reaction, the hydrogen bond interaction between allylic alcohols and sulfinic acids allowed for reciprocal activation, which enabled a dehydrative cross-coupling process to occur under mild reaction conditions. This reaction worked in an environmentally friendly manner, yielding water as the only byproduct. A variety of allylic sulfones could be obtained in good to excellent yields with wide functional group tolerance. In gram scale reactions, allylic sulfones could be conveniently isolated in high yield by filtration.
Direct substitution of primary allylic amines with sulfinate salts
Wu, Xue-Song,Chen, Yan,Li, Man-Bo,Zhou, Meng-Guang,Tian, Shi-Kai
supporting information, p. 14694 - 14697 (2012/11/07)
The NH2 group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl]2, 0.4 mol % 1,4- bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1′-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.
α-Sulfonyl succinimides: Versatile sulfinate donors in Fe-catalyzed, salt-free, neutral allylic substitution
Jegelka, Markus,Plietker, Bernd
, p. 10417 - 10430 (2011/10/31)
Allyl sulfones are versatile intermediates in organic chemistry. The presence of two distinct functional groups sets the stage for a plethora of subsequent transformations. However, despite these advantages the preparation of regioisomerically enriched sulfones is not easy. The use of sulfinate salts as nucleophiles in substitutions is frequently accompanied by side reactions such as π-bond migration, β-elimination, and so on. Herein we present a preparatively simple way to synthesize a variety of different aryl or alkyl allyl sulfones starting from readily accessible allylic carbonates. By employing aryl or alkyl α-sulfonyl succinimides as sulfinate synthons, mild and regioselective ipso substitution of diverse allylic carbonates was realized.
Synthesis by SO2 Extrusion: Photochemical and Thermal Reactions of Cinnamyl Benzyl Sulfone
Wylie, Philip L.,Prowse, K. Spencer,Belill, Mark A.
, p. 4022 - 4025 (2007/10/02)
The photochemistry and pyrolytic behavior of trans-cinnamyl benzyl sulfone have been investigated.Direct photolysis in benzene gives high yields of the SO2 extrusion products 3,4-diphenyl-1-butene and cis- and trans-1,4-diphenyl-1-butene.Addition of trans-piperylene to the photolysis substantially reduces the amount of cis-1,4-diphenyl-1-butene formed.Photolysis in acetone gives primarily trans-cis isomerization, though minor amounts of the SO2 extrusion products and bibenzyl were also formed.Flash vacuum pyrolysis of cinnamyl benzyl sulfone gave only minor amounts o f the SO2 extrusion products; these were shown to be unstable under the conditions of pyrolysis.Instead, indene, styrene, bibenzyl, and toluene were formed.Pyrolysis of 1,4-diphenyl-1-butene gave these same products.
