131719-40-9Relevant academic research and scientific papers
Stereodivergent Hydroboration of Allenes
Nagashima, Yoshiyuki,Sasaki, Keiji,Suto, Takahiro,Sato, Takaaki,Chida, Noritaka
supporting information, p. 1024 - 1028 (2018/03/21)
Full details of a stereodivergent hydroboration of allenes are reported. While hydroboration of an allene with 9-BBN provided a thermodynamically stable (E)-allylic alcohol after oxidative work-up, the reaction of an identical allene with HB(Sia)2 (disiamylborane) formed a (Z)-allylic alcohol as the kinetic product. The developed conditions allowed for the synthesis of trisubstituted olefins in a highly stereoselective fashion, which is known to be challenging. The method was also applied to the stereodivergent synthesis of structural motifs such as skipped dienes and allylbenzenes, which are often embedded in biologically active natural products.
Asymmetric construction of quaternary stereogenic centers via auxiliary-based SN2′ reactions: A case of 1,7-relative stereogenesis
Denmark, Scott E.,Marble, Lyndon K.
, p. 559 - 590 (2016/11/15)
The stereoselective construction of quaternary stereogenic centers is described that employs an allylic substitution through the intermediacy of a chiral carbamate leaving group. Five carbamates with two substituents at the allylic terminus combined with
Rhenium-catalyzed 1,3-isomerization of allylic alcohols: Scope and chirality transfer
Morrill, Christie,Beutner, Gregory L.,Grubbs, Robert H.
, p. 7813 - 7825 (2007/10/03)
(Chemical Equation Presented) The scope of the triphenylsilyl perrhennate (O3ReOSiPh3, 1) catalyzed 1,3-isomerization of allylic alcohols has been thoroughly explored. It was found to be effective for a wide variety of secondary and tertiary allylic alcohol substrates bearing aryl, alkyl, and cyano substituents. Two general reaction types were found which gave high levels of product selectivity: those driven by formation of an extended conjugated system and those driven by selective silylation of a particular isomer. The efficiency of chirality transfer with various substrates was investigated, and conditions were found in which secondary and tertiary allylic alcohols could be formed with high levels of enantioselectivity. Consideration of selectivity trends with respect to the nature of the substituents around the allylic system revealed that this is a reliable and predictable method for allylic alcohol synthesis.
Highly selective 1,3-isomerization of allylic alcohols via rhenium oxo catalysis
Morrill, Christie,Grubbs, Robert H.
, p. 2842 - 2843 (2007/10/03)
Two reaction strategies are developed to promote the highly selective 1,3-isomerization of a variety of allylic alcohols using O3ReOSiPh3 as a catalyst. The first strategy utilizes substrates whose 1,3-regioisomer contains a conjugated alkene, which relies on thermodynamics to obtain high selectivity. The second strategy employs N,O-bis(trimethylsilyl)acetamide as an additive to selectively and irreversibly remove the product from the reaction equilibrium and works well for the isomerization of tertiary allylic alcohols into primary allylic alcohols containing trisubstituted alkene components. High stereoselectivity is also observed in the 1,3-isomerization of enantioenriched allylic alcohols. Copyright
