- Palladium-Catalyzed Three-Component Reaction of 3-(Tri-n- butylstannyl)allyl Acetates, Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ-Substituted Allylic Tin Reagents
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A three-component reaction of 3-(tri-n-butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium-Xantphos catalyst system predominately gave (E)-anti-homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem-palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in-situ-generated (E)-vinylpalladium acetate with the triorganoborane.
- Horino, Yoshikazu,Sugata, Miki,Abe, Hitoshi
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supporting information
p. 1023 - 1028
(2016/04/19)
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- Pd-catalyzed three-component reaction of 3-(Pinacolatoboryl)ally acetates, aldehydes, and organoboranes: A new entry to stereoselective synthesis of (Z)- anti -homoallylic alcohols
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The Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl acetates, aldehydes, and organoboranes is described. The reaction is initiated by the formation of an allylic gem-palladium/boryl intermediate, which then undergoes allylation of aldehydes by allylboronates followed by a coupling reaction of in situ generated (Z)-vinylpalladium acetates with organoboranes to provide the (Z)-anti-homoallylic alcohols with high levels of diastereoselectivity and alkene stereocontrol.
- Horino, Yoshikazu,Aimono, Ataru,Abe, Hitoshi
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supporting information
p. 2824 - 2827
(2015/06/16)
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- Divergence from the classical hydroboration reactivity; boron containing materials through a hydroboration cascade of small cyclic dienes
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The hydroboration 1,3- and 1,4-cyclic dienes has been systematically investigated. The behavior of such dienes towards mono and dihydroboration was monitored directly by 11B NMR to identify the actual boron species formed, as opposed to the most common analysis of the resultant oxidation products. Quantitative dihydroboration was achieved for the full range of cyclic dienes investigated including dienes, which were previously reported to be resistant to dihydroboration, leading to the formation of new boron-containing polymeric materials. The conditions favoring dihydroboration are reported as well as full characterisation of the materials. Furthermore, a hydroboration cascade mechanism is proposed for the formation of such boron-containing polymers, supported by both experimental and theoretical data.
- Andreou, Anna,Leskes, Michal,Jambrina, Pablo G.,Tustin, Gary J.,Grey, Clare P.,Rosta, Edina,Scherman, Oren A.
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p. 6262 - 6269
(2015/10/28)
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- Generation of organolithium compounds bearing super silyl ester and their application to Matteson rearrangement
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It's super-silyl-fragilithyl-ester-aryl-docious: The super silyl group is a strong protecting group for carboxylic acids and provides a method for direct lithiation that is compatible with the ester moiety. Organolithium compounds bearing a super silyl ester react with a variety of electrophiles in high yields (see scheme). The reaction of lithiated super silyl chloroacetate with a boron compound gives α-functionalization of the ester moiety by Matteson rearrangement. Copyright
- Oda, Susumu,Yamamoto, Hisashi
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supporting information
p. 8165 - 8168
(2013/08/23)
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- Ferrocenylhydridoborates: Synthesis, structural characterization, and application to the preparation of ferrocenylborane polymers
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Mono- and ditopic lithium ferrocenylhydridoborates Li[FcBH3] (2) and Li2[H3B-fc-BH3] (4) have been synthesized from FcB(OMe)2/(MeO)2B-fc-B(OMe)2 and Li[AlH4] (Fc = fer
- Scheibitz, Matthias,Li, Haiyan,Schnorr, Jan,Perucha, Alejandro Sanchez,Bolte, Michael,Lerner, Hans-Wolfram,Jaekle, Frieder,Wagner, Matthias
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p. 16319 - 16329
(2010/02/16)
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- On titanium-promoted hydroborations of alkenes by borohydride and by catecholborane
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Some literature reports of catalyzed hydroborations of alkenes by the borohydride anion and by catecholborane were investigated to probe the actual mode of hydroboration. Reactions involving both TiCl3 and Ti(OiPr)4 seems to involve predominantly formation of BH3 in situ, although there is some evidence that the metal may be directly involved in a few cases. Ambiguity arises because it is shown that alkyl boronate esters can be formed by exchange between catecholborane and alkylboranes, so formation of these esters is not firm evidence of catalysis.
- Burgess, Kevin,Van Der Donk, Wilfred A.
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p. 3616 - 3620
(2008/10/08)
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- Reaction of organoboranes with hydrazoic acid
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Organoboranes react with sodium azide in the presence of aqueous acid to yield primary amines. The reaction presumably proceeds via the anionotropic rearrangement of an organoborate complex.
- Kabalka, George W.,Henderson, David A.,Varma, Rajender S.
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p. 1369 - 1370
(2008/10/08)
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