Direct Dehydroxylative Coupling Reaction of Alcohols with Organosilanes through Si–X Bond Activation by Halogen Bonding

Saito, Masato; Tsuji, Nobuya; Kobayashi, Yusuke; Takemoto, Yoshiji

doi:10.1021/acs.orglett.5b01290

Cited by 96 publications

(53 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1,5] We thus focused on halogen bonding (XB), which is anoncovalent interaction between halogenated compounds and Lewis bases. As expected, the 2-iodoimidazolium-and 2-iodobenzimidazolium-type XB donors [13][14][15][16][17][18] 4 and 5 efficiently promoted the umpolung CÀC Scheme 1. [16,17] We envisaged that the soft Lewis acidity of XB donors [18][19][20] would allow them to preferentially interact with soft electrophiles (Scheme 1c).…”

supporting

confidence: 78%

“…[6] Many approaches have been investigated for the synthesis of these important synthetic intermediates; [7][8][9][10] however,t he activation of the iodonium ylide seems to be the most challenging aspect of such ah ypothetical reaction. [16,17] We envisaged that the soft Lewis acidity of XB donors [18][19][20] would allow them to preferentially interact with soft electrophiles (Scheme 1c). [1,5] We thus focused on halogen bonding (XB), which is anoncovalent interaction between halogenated compounds and Lewis bases.…”

mentioning

confidence: 99%

“…[1,5] We thus focused on halogen bonding (XB), which is anoncovalent interaction between halogenated compounds and Lewis bases. [16,17] We envisaged that the soft Lewis acidity of XB donors [18][19][20] would allow them to preferentially interact with soft electrophiles (Scheme 1c). [16,17] We envisaged that the soft Lewis acidity of XB donors [18][19][20] would allow them to preferentially interact with soft electrophiles (Scheme 1c).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Electrophilic Activation of Iodonium Ylides by Halogen‐Bond‐Donor Catalysis for Cross‐Enolate Coupling

et al. 2017

Self Cite

View full text Add to dashboard Cite

The umpolung alkylation of silyl enol ethers with an iodonium(III) ylide proceeds under mild conditions to afford various 1,4-dicarbonyl compounds in high yields in the presence of ah alogen-bonding catalyst. Unlike typical transition-metal activation processes of such ylide precursors, which tend to proceed via carbenoid intermediates,e xperimental and computational studies indicate that halogen bonding (XB) between the XB donor catalyst and the iodonium ylide plays ac rucial role in promoting the reaction. The identification of ac ompatible Bronsted base catalyst enabled the extension of this method to enols generated in situ to give the corresponding adducts in good yields.Hypervalent iodine compounds have become essential in organic synthesis because avariety of oxidation and oxidative bond-forming reactions can be achieved with these reagents. [1] In particular, recent advances in the use of iodonium(III) salts have enabled the a-functionalization of various carbonyl compounds under mild conditions.I nt hese reactions, ac opper(I) catalyst [2] or as toichiometric amount of acid [3] is used to activate the iodonium salt (Scheme 1a). Compared with a-arylation and a-alkynylation, C(sp 3 )ÀC(sp 3 )b ondforming reactions [4] are less well developed, despite the utility of the resulting products. [1][2][3] We envisioned that the crosscoupling of an iodonium(III) ylide [1,5] with carbonyl compounds would enable C(sp 3 ) À C(sp 3 )b ond formation and provide 1,4-dicarbonyl compounds (Scheme 1c), which are found in av ariety of important natural product scaffolds or used for their preparation. [6] Many approaches have been investigated for the synthesis of these important synthetic intermediates; [7][8][9][10] however,t he activation of the iodonium ylide seems to be the most challenging aspect of such ah ypothetical reaction. This is the result of their facile decomposition, insertion, and transylidation in the presence of hard Lewis acids, [5,11] even though such reactions generally occur via metal carbenoids in the presence of rhodium or copper catalysts (Scheme 1b). [1,5] We thus focused on halogen bonding (XB), which is anoncovalent interaction between halogenated compounds and Lewis bases. [12] Although XB donors have recently begun to be used in synthetic organic chemistry as easy-to-handle organic Lewis acids, [13] their activation mode is mainly limited to the sp 2 -hybridized nitrogen atoms of quinolines and imines, [14] carbonyl oxygen atoms, [15] and alkyl halides. [16,17] We envisaged that the soft Lewis acidity of XB donors [18][19][20] would allow them to preferentially interact with soft electrophiles (Scheme 1c). Herein, we report the first efficient electrophilic activation of iodonium(III) ylides for which an XB donor was found to be effective.I na ddition, we have developed the first XB donor/Brønsted base cooperative catalytic system, which enabled the in situ formation of the nucleophilic component without deactivation of the XB donor catalyst.First, we studied the interaction between XB donors ...

show abstract

supporting

confidence: 78%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Electrophilic Activation of Iodonium Ylides by Halogen‐Bond‐Donor Catalysis for Cross‐Enolate Coupling

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Thus, in 2015, Takemoto and co-workers described a halogen bond donor-catalyzed dehydroxylative coupling reaction of benzyl alcohols and allyltrimethylsilane (Scheme 21) [92]. …”

Section: Reviewmentioning

confidence: 99%

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

Nagorny¹,

Sun²

2016

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

show abstract

“…In 2015, Takemoto and co-workers developed a combination of a halogen bond (XB) donor with trimethyl-silyl halide (TMSX) as an efficient cocatalytic system for the direct dehydroxylative coupling reaction of alcohol with different nucleophiles bearing TMS groups, such as allyltrimethylsilane and trimethylsilylcyanide, to provide the corresponding adduct 197 whereas, in 2016 an effective method for cross-coupling of heteroaryl boronic acids with allylic alcohols under catalyst-free reaction conditions was reported. 198 Onaka and co-workers developed a new method to transform natural montmorillonite into a solid acid catalyst employing a catalytic amount of TMSCl.…”

mentioning

confidence: 99%

Alcohols in direct carbon-carbon and carbon-heteroatom bond-forming reactions: recent advances

Ajvazi¹,

Stavber²

2018

Arkivoc

View full text Add to dashboard Cite

In recent years, nucleophilic substitution of alcohols leading to the formation of the C-C and C-heteroatom bonds has become an attractive process used in the synthesis of organic compounds, offering a potential impact on the environment, since water is the only by-product of the reaction. A comprehensive compilation of methods for the activation and displacement of a hydroxyl group covering the last seventeen years is the objective of the present review.

show abstract

Direct Dehydroxylative Coupling Reaction of Alcohols with Organosilanes through Si–X Bond Activation by Halogen Bonding

Cited by 96 publications

References 60 publications

Electrophilic Activation of Iodonium Ylides by Halogen‐Bond‐Donor Catalysis for Cross‐Enolate Coupling

Electrophilic Activation of Iodonium Ylides by Halogen‐Bond‐Donor Catalysis for Cross‐Enolate Coupling

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

Alcohols in direct carbon-carbon and carbon-heteroatom bond-forming reactions: recent advances

Contact Info

Product

Resources

About