137120-08-2Relevant academic research and scientific papers
Synthetic approach to the AB ring system of ouabain
Jung, Michael E.,Piizzi, Grazia
, p. 2572 - 2582 (2003)
Several novel hydroxylated cis-decalin derivatives, potential intermediates for the synthesis of the AB ring system of the important cardiotonic steroid ouabain, have been synthesized from commercially available starting materials. The first step in the preparation of these highly functionalized intermediates is a Robinson annulation of the β-keto ester 6 and the 4-silyl-3-buten-2-one 5 to furnish the octalone 4 with good diastereoselectivity in fair yield (due to competition with a novel silicon-to-carbon phenyl migration). Reduction of the epoxy alcohol 3 (derived from 4 in two high-yielding steps) with LiAlH4 gave a mixture of the desired triol 11 along with the product of an unusual reductive opening at the tertiary carbon, namely the triol 12. A plausible mechanism for this unusual reduction is presented as are possible methods for avoiding it. In particular, reduction of the corrresponding epoxy ketone 15 with aluminum amalgam proceeded in good yield to give the hydroxy ketone 16. Also reduction of the epoxide ester having the inverted stereochemistry at C3 afforded the desired tertiary alcohol 33 in good yield. Another approach using the β,γ-unsaturated ketal 38 permitted the formation of the tertiary alcohol 40. Fleming oxidation of the related, very functionalized silane 39 afforded the desired 1β-alcohol 41 in fair yield. Finally a novel rearrangement was observed when the epoxy alcohol 24 was treated with DIBAL to effect loss of the angular hydroxymethyl group to produce the tetrasubstitued alkene 29 in high yield.
A recyclable and reusable K2PtCl4/Xphos-SO3Na/PEG-400/H2O system for highly regio- and stereoselective hydrosilylation of terminal alkynes
Xu, Caifeng,Huang, Bin,Yan, Tao,Cai, Mingzhong
supporting information, p. 391 - 397 (2018/02/07)
K2PtCl4/Xphos-SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly regio- and stereoselective catalyst for the hydrosilylation of terminal alkynes with hydrosilanes. The reaction could be conducted under mild conditions, yielding a variety of functionalized β-(E)-vinylsilanes in good to excellent yields with a total β-(E)-selectivity. The isolation of the products is readily performed by extraction with cyclohexane and more importantly, both expensive K2PtCl4 and Xphos-SO3Na in a PEG-400/H2O system could be easily recycled and reused at least eight times without any loss of catalytic activity.
Enantioselective NiH/Pmrox-Catalyzed 1,2-Reduction of α,β-Unsaturated Ketones
Chen, Fenglin,Zhang, Yao,Yu, Lei,Zhu, Shaolin
supporting information, p. 2022 - 2025 (2017/02/15)
The enantioselective 1,2-reduction of α,β-unsaturated ketones was achieved using a NiH catalyst in the presence of pinacolborane. This mild process represents a general method to access a wide variety of structurally diverse α-chiral allylic alcohols in excellent yields and enantioselectivity, as well as very high levels of ambidoselectivity for 1,2- over 1,4-reduction. Furthermore, for reactions on a 10 mmol scale, catalyst loadings as low as 0.5 mol % could be employed to deliver product without any detrimental effect on the yield, enantio-, or ambidoselectivity.
Copper-Catalyzed γ-Selective and Stereospecific Allylic Cross-Coupling with Secondary Alkylboranes
Yasuda, Yuto,Nagao, Kazunori,Shido, Yoshinori,Mori, Seiji,Ohmiya, Hirohisa,Sawamura, Masaya
supporting information, p. 9666 - 9670 (2015/06/30)
The scope of the copper-catalyzed coupling reactions between organoboron compounds and allylic phosphates is expanded significantly by employing triphenylphosphine as a ligand for copper, allowing the use of secondary alkylboron compounds. The reaction proceeds with complete γ-E-selectivity and preferential 1,3-syn stereoselectivity. The reaction of γ-silicon-substituted allylic phosphates affords enantioenriched α-stereogenic allylsilanes.
Platinum catalysed hydrosilylation of propargylic alcohols
McAdam, Catherine A.,McLaughlin, Mark G.,Johnston, Adam J. S.,Chen, Jun,Walter, Magnus W.,Cook, Matthew J.
, p. 4488 - 4502 (2013/08/23)
A facile and user-friendly protocol has been developed for the selective synthesis of E-vinyl silanes derived from propargylic alcohols using a PtCl 2/XPhos catalyst system. The reaction is generally high yielding and provides a single regioiso
Reversible 1,3-anti/syn-stereochemical courses in copper-catalyzed γ-selective allyl-alkyl coupling between chiral allylic phosphates and alkylboranes
Nagao, Kazunori,Yokobori, Umi,Makida, Yusuke,Ohmiya, Hirohisa,Sawamura, Masaya
supporting information; scheme or table, p. 8982 - 8987 (2012/07/02)
The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with γ-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.
PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols
McLaughlin, Mark G.,Cook, Matthew J.
supporting information; experimental part, p. 11104 - 11106 (2011/11/07)
A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl2/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.
Mechanistic studies of the allylic rearrangements of α-silyloxy allylic silanes to silyloxy vinylic silanes
Kim, Angie I.,Kimmel, Kyle L.,Romero, Antonio,Smitrovich, Jacqueline H.,Woerpel
, p. 6595 - 6598 (2008/02/10)
(Chemical Equation Presented) Mechanistic evidence suggests that the Lewis acid-promoted allylic rearrangement of α-silyloxy allylic silanes proceeds along an ionic reaction pathway involving a contact ion pair. The driving force for this transformation i
Novel rearrangements of 4-silyl-3-buten-2-ones
Jung, Michael E.,Piizzi, Grazia
, p. 3911 - 3914 (2007/10/03)
Two-4-silyl-3-buten-2-ones, 2a, and 2c, underwent an interesting rearrangement involving migration of the allyl or phenyl group on the silicon atom to the adjacent enone carbon when treated with various bases.
Stereoselective synthesis of (Z)- and (E)-allylic silanes by copper- mediated substitution reactions of allylic carbamates with grignard reagents
Smitrovich, Jacqueline H.,Woerpel
, p. 1601 - 1614 (2007/10/03)
Both (Z)- and (E)-allylic silanes were prepared with high stereoselectivity by the copper-mediated substitution of allylic carbamates by organometallic reagents. The reaction of alkylmagnesium reagents with (E)- allylic carbamates provides (Z)-allylic silanes, whereas both alkylmagnesium and alkyllithium reagents react with (Z)-allylic carbamates to afford (E)- allylic silanes. Because Grignard reagents are often more facile to prepare than alkyllithium species, these reagents are the optimal nucleophiles for the synthesis of both (Z)- and (E)-allylic silanes. This method also allows readily available nonracemic allylic carbamates to be converted to chiral, nonracemic (Z)- and (E)-allylic silanes with high stereoselectivity.
