80989-84-0Relevant articles and documents
One-Pot Synthesis of Strain-Release Reagents from Methyl Sulfones
Jung, Myunggi,Lindsay, Vincent N. G.
supporting information, p. 4764 - 4769 (2022/04/07)
Sulfone-substituted bicyclo[1.1.0]butanes and housanes have found widespread application in organic synthesis due to their bench stability and high reactivity in strain-releasing processes in the presence of nucleophiles or radical species. Despite their increasing utility, their preparation typically requires multiple steps in low overall yield. In this work, we report an expedient and general one-pot procedure for the synthesis of 1-sulfonylbicyclo[1.1.0]butanes from readily available methyl sulfones and inexpensive epichlorohydrin via the dialkylmagnesium-mediated formation of 3-sulfonylcyclobutanol intermediates. Furthermore, the process was extended to the formation of 1-sulfonylbicyclo[2.1.0]pentane (housane) analogues when 4-chloro-1,2-epoxybutane was used as the electrophile instead of epichlorohydrin. Both procedures could be applied on a gram scale with similar efficiency and are shown to be fully stereospecific in the case of housanes when an enantiopure epoxide was employed, leading to a streamlined access to highly valuable optically active strain-release reagents.
Photochemical Strain-Release-Driven Cyclobutylation of C(sp3)-Centered Radicals
Ernouf, Guillaume,Chirkin, Egor,Rhyman, Lydia,Ramasami, Ponnadurai,Cintrat, Jean-Christophe
, p. 2618 - 2622 (2019/11/19)
A new photoredox-catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese-type addition of C(sp3)-centered radicals to highly strained bicyclo[1.1.0]but
DISULFIDE BIOCONJUGATION
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, (2018/11/22)
Compounds and methods are provided for one-step functionalization of disulfide bonds in proteins.
Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors
Wu, Xiangyu,Hao, Wei,Ye, Ke-Yin,Jiang, Binyang,Pombar, Gisselle,Song, Zhidong,Lin, Song
supporting information, p. 14836 - 14843 (2018/11/10)
Alkyl chlorides are common functional groups in synthetic organic chemistry. However, the engagement of unactivated alkyl chlorides, especially tertiary alkyl chlorides, in transition-metal-catalyzed C-C bond formation remains challenging. Herein, we describe the development of a TiIII-catalyzed radical addition of 2° and 3° alkyl chlorides to electron-deficient alkenes. Mechanistic data are consistent with inner-sphere activation of the C-Cl bond featuring TiIII-mediated Cl atom abstraction. Evidence suggests that the active TiIII catalyst is generated from the TiIV precursor in a Lewis-acid-assisted electron transfer process.
Organic chemistry: Strain-release amination
Gianatassio, Ryan,Lopchuk, Justin M.,Wang, Jie,Pan, Chung-Mao,Malins, Lara R.,Prieto, Liher,Brandt, Thomas A.,Collins, Michael R.,Gallego, Gary M.,Sach, Neal W.,Spangler, Jillian E.,Zhu, Huichin,Zhu, Jinjiang,Baran, Phil S.
, p. 241 - 246 (2016/01/25)
To optimize drug candidates, modern medicinal chemists are increasingly turning to an unconventional structural motif: small, strained ring systems. However, the difficulty of introducing substituents such as bicyclo[1.1.1]pentanes, azetidines, or cyclobutanes often outweighs the challenge of synthesizing the parent scaffold itself. Thus, there is an urgent need for general methods to rapidly and directly append such groups onto core scaffolds. Here we report a general strategy to harness the embedded potential energy of effectively spring-loaded C-C and C-N bonds with the most oft-encountered nucleophiles in pharmaceutical chemistry, amines. Strain-release amination can diversify a range of substrates with a multitude of desirable bioisosteres at both the early and late stages of a synthesis. The technique has also been applied to peptide labeling and bioconjugation.
NEW BRIDGEHEAD-SUBSTITUTED 1-(ARYLSULFONYL)BICYCLOBUTANES AND SOME NOVEL ADDITION REACTIONS OF THE BICYCLIC SYSTEM
Gaoni, Yehiel
, p. 2819 - 2840 (2007/10/02)
In view of planned syntheses of target cyclobutane derivatives, a series of new 3-substituted bicyclobutanes was prepared from sulfones 1-7.Some novel addition reactions involving the central bond were then applied to several of the new compounds as well
Preparation of Ring-Substituted (Arylsulfonyl)cyclopropanes and (Arylsulfonyl)bicyclobutanes from γ,δ-Epoxy Sulfones
Gaoni, Yehiel
, p. 2564 - 2571 (2007/10/02)
Treatment of γ,δ-epoxy sulfones 2 with n-butyllithium provides 1-(hydroxyalkyl)-2-(arylsulfonyl)cyclopropanes (3).Dehydration of the latter, when applicable, yields 1-alkenyl-2-(arylsulfonyl)cyclopropanes (5) which can be epoxidized and converted by a sec
A SIMPLE ONE-POT PREPARATION OF 1-ARYLSULFONYLBICYCLOBUTANES FROM γ,δ-EPOXYSULFONES
Gaoni, Yehiel
, p. 4339 - 4340 (2007/10/02)
Sequential treatment of γ,δ-epoxysulfones with butyl lithium, methanesulfonyl chloride, and butyl lithium provides 1-arylsulfonylbicyclobutanes in over 50percent overall yields.
