112571-33-2Relevant academic research and scientific papers
Chiral Synthesis via Organoboranes. 13. A Highly Diastereoselective and Enantioselective Addition of diisopinocampheylboranes to Aldehydes
Brown, Herbert C.,Jadhav, Prabhakar K.,Bhat, Krishna S.
, p. 1535 - 1538 (1988)
Isomerically pure diisopinocampheylboranes have been prepared from B-methoxydiisopinocampheylborane and lithiated allyl methyl ether.These enantiomeric diisopinocamphpeylboranes, the first such derivatives to be synthesized, retain their stereochemical identity under the reaction conditions.They have been succesfully condensed with various aldehydes, such as acetaldehyde, propionaldehyde, 2-methylpropionaldehyde, and benzaldehyde in a regioselective and stereoselective manner to yield the corresponding threo-β-methoxyhomoallyl alcohols in >/= 99percent diastereoselectivities and >/= 95percent enantioselectivities.Similarly, diisocampheylborane (3) was prepared and was utilized for the preparation of threo-1,2-diol.
Highly functionalized tertiary- carbinols and carbinamines from the asymmetric γ-alkoxyallylboration of ketones and ketimines with the borabicyclodecanes
Munoz-Hernandez, Lorell,Seda, Luis A.,Wang, Bo,Soderquist, John A.
, p. 4052 - 4055 (2014)
The first asymmetric γ-alkoxyallylboration of representative ketones provides β-alkoxy tert-homoallylic alcohols 10 whose diastereoselectivities range from 99% syn (acetophenone) to 99% anti (pinacolone) both with high ee (>95%). This distribution is attributable to the c/t isomerization of the BBD reagents and the greater reactivity of 7 vs 1 and of aromatic vs alkyl ketones. A ketone-based direct synthesis of a fostriecin intermediate and the tert-amine 26 are reported, each with high selectivities.
Catalytic Allylation of Aldehydes Using Unactivated Alkenes
Tanabe, Shun,Mitsunuma, Harunobu,Kanai, Motomu
supporting information, p. 12374 - 12381 (2020/07/14)
Simple feedstock organic molecules, especially alkenes, are attractive starting materials in organic synthesis because of their wide availability. Direct utilization of such bulk, inert organic molecules for practical and selective chemical reactions, however, remains limited. Herein, we developed a ternary hybrid catalyst system comprising a photoredox catalyst, a hydrogen-atom-transfer catalyst, and a chromium complex catalyst, enabling catalytic allylation of aldehydes with simple alkenes, including feedstock lower alkenes. The reaction proceeded under visible-light irradiation at room temperature and with high functional group tolerance. The reaction was extended to an asymmetric variant by employing a chiral chromium complex catalyst.
Ni- and pd-catalyzed synthesis of substituted and functionalized allylic boronates
Zhang, Ping,Roundtree, Ian A.,Morken, James P.
supporting information; experimental part, p. 1416 - 1419 (2012/06/01)
Two highly efficient and convenient methods for the synthesis of functionalized and substituted allylic boronates are described. In one procedure, readily available allylic acetates are converted to allylic boronates catalyzed by Ni/PCy3 or Ni/PPh3 complexes with high levels of stereoselectivity and in good yields. Alternatively, the borylation can be accomplished with commercially available Pd catalysts [e.g., Pd 2(dba)3, PdCl2, Pd/C], starting with easily accessed allylic halides.
Asymmetric γ-methoxyallylation with the robust 10-tms-9- borabicyclo[3.3.2]decanes
Munoz-Hernandez, Lorell,Soderquist, John A.
supporting information; experimental part, p. 2571 - 2574 (2009/10/23)
The asymmetric γ-methoxyallylboration of aldehydes with the configurationally very stable 1 gives nonracemic threo-β-methoxyhomoallylic alcohols 7 (65-93%) with excellent selectivity (96-99% de, 98-99% ee). The corresponding homoallylic amines 10 are obta
Diastereoselective synthesis of unsaturated 1,2-amino alcohols from α-hydroxy allyl ethers using chlorosulfonyl isocyanate
Kim, Ji Duck,Kim, In Soo,Hua, Jin Cheng,Zee, Ok Pyo,Jung, Young Hoon
, p. 1079 - 1082 (2007/10/03)
Diastereoselective synthesis of 1,2-amino alcohols was achieved from a highly diastereoselective allylic amination reaction of α-hydroxy allyl ethers using chlorosulfonyl isocyanate. Diastereoselectivities varied depending on the stereochemistry of the ethers used and the stability of the carbocation intermediate obtained during the reaction. We propose that this CSI reaction is the results of either a SNi or SN1 mechanism, according to the stability of the carbocation intermediate.
Cytochrome P450-catalyzed hydroxylation of mechanistic probes that distinguish between radicals and cations. Evidence for cationic but not for radical intermediates
Newcomb, Martin,Shen, Runnan,Choi, Seung-Yong,Toy, Patrick H.,Hollenberg, Paul F.,Vaz, Alfin D. N.,Coon, Minor J.
, p. 2677 - 2686 (2007/10/03)
Oxidation of the mechanistic probes trans,trans-2-methoxy-3- phenylmethylcyclopropane and methylcubane by six cytochrome P450 isozymes has been studied. The probes differentiate between radical and cationic species in that different structural rearrangeme
Bu4NF-BF3*Et2O as a New Reagent for the Selective Deprotection of the Enol Ethers of γ-Alkoxyallylstannanes
Gevorgyan, Vladimir,Yamamoto, Yoshinori
, p. 59 - 60 (2007/10/02)
The combination of Bu4NF-BF3*Et2O deprotects selectively the enol ether protecting group of γ-alkoxy- and benzyloxy-allyltributylstannanes, without destannylating the tributylstannyl group, affording the corresponding γ-tributylstannyl aldehyde in high yield.
REDUCTION OF ACROLEIN DIALKYL ACETALS WITH CrCl2. γ-ALKOXY SUBSTITUTED ALLYLIC CHROMIUM REAGENTS FOR SELECTIVE SYNTHESIS OF erythro-1,2-DIOLS.
Takai, Kazuhiko,Nitta, Kenji,Utimoto, Kiitiro
, p. 5263 - 5266 (2007/10/02)
Treatment of an aldehyde in THF at -30 deg C with a reagent derived by reduction of acrolein dialkyl acetal with CrCl2 in the presence of Me3SiI gave 1,2-erythro-3,4-butene-1,2-diol derivatives selectively.
