Approximation to an enantioselective synthesis of helicenes and other chiral nanographenes
Authorship
M.B.L.
Master in Organic Chemistry (3ª ed)
M.B.L.
Master in Organic Chemistry (3ª ed)
Defense date
09.18.2025 10:00
09.18.2025 10:00
Summary
Asymmetric synthesis of chiral polycyclic aromatic hydrocarbons (PAHs) and chiral nanographenes has attracted growing interest due to the unique optoelectronic properties this type of molecules, that can be applied tothe development of chiroptical materials. Our research group is expert in the development of synthetic methodology for PAHs and nanographenes by aryne-based chemistry, having discovered the palladium-catalyzed [2+2+2] cycloadditions of arynes, including one example of asymmetric catalysis for the synthesis of a pentahelicene. In this context, this work is aimed to study the access to chiral, sterically congested nanographenes by palladium-catalyzed [2+2+2] cycloaddition reactions of arynes, including an approach to the development of asymetric versions. In particular, the synthesis of a [7]helicene and a 5,8,17,18-tetraphenyltetrabenzo[a,c,m,o]pentaphene was attempted, by means of cycloaddition reactions of DMAD with 3-phenenthryne and 1,4-diphenyl-2-triphenylyne, respectively. In addition, it is also developed the synthesis and optimization of a new precursor of this polycyclic aryne in just three steps.
Asymmetric synthesis of chiral polycyclic aromatic hydrocarbons (PAHs) and chiral nanographenes has attracted growing interest due to the unique optoelectronic properties this type of molecules, that can be applied tothe development of chiroptical materials. Our research group is expert in the development of synthetic methodology for PAHs and nanographenes by aryne-based chemistry, having discovered the palladium-catalyzed [2+2+2] cycloadditions of arynes, including one example of asymmetric catalysis for the synthesis of a pentahelicene. In this context, this work is aimed to study the access to chiral, sterically congested nanographenes by palladium-catalyzed [2+2+2] cycloaddition reactions of arynes, including an approach to the development of asymetric versions. In particular, the synthesis of a [7]helicene and a 5,8,17,18-tetraphenyltetrabenzo[a,c,m,o]pentaphene was attempted, by means of cycloaddition reactions of DMAD with 3-phenenthryne and 1,4-diphenyl-2-triphenylyne, respectively. In addition, it is also developed the synthesis and optimization of a new precursor of this polycyclic aryne in just three steps.
Direction
Pérez Meirás, María Dolores (Tutorships)
Pérez Meirás, María Dolores (Tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
Synthesis of Vitamin D3 Analogues with an m-Carborane Unit in the Side Chain
Authorship
A.T.T.
Master in Organic Chemistry (3ª ed)
A.T.T.
Master in Organic Chemistry (3ª ed)
Defense date
09.18.2025 10:00
09.18.2025 10:00
Summary
As part of a program aimed at the design and synthesis of 1,25D3 hormone analogues containing carborane units in the side chain, with potential utility for cancer therapy through the use of BNCT (Boron Neutron Capture Therapy), compound 1 was designed via docking calculations and synthesized from the Inhofen-Lythgoe diol in 17 steps with an overall yield of 9%. This compound shows potential utility in the treatment of hyperproliferative diseases or as an antagonist ligand of the VDR (Vitamin D Receptor). The synthesis of benzoate 2 was also carried out in order to study its chemistry and biological behavior. The active form of vitamin D3 is 1a,25-dihydroxyvitamin D3 (Figure 1), also called calcitriol. It regulates calcium and phosphorus levels in the intestine, liver, and bones, and plays an important role in cell differentiation and in the inhibition of cell proliferation, as well as in the regulation of the immune system. Nutritional deficiency has also been observed to cause rickets.
As part of a program aimed at the design and synthesis of 1,25D3 hormone analogues containing carborane units in the side chain, with potential utility for cancer therapy through the use of BNCT (Boron Neutron Capture Therapy), compound 1 was designed via docking calculations and synthesized from the Inhofen-Lythgoe diol in 17 steps with an overall yield of 9%. This compound shows potential utility in the treatment of hyperproliferative diseases or as an antagonist ligand of the VDR (Vitamin D Receptor). The synthesis of benzoate 2 was also carried out in order to study its chemistry and biological behavior. The active form of vitamin D3 is 1a,25-dihydroxyvitamin D3 (Figure 1), also called calcitriol. It regulates calcium and phosphorus levels in the intestine, liver, and bones, and plays an important role in cell differentiation and in the inhibition of cell proliferation, as well as in the regulation of the immune system. Nutritional deficiency has also been observed to cause rickets.
Direction
PAZ CASTAÑAL, MANUEL MARIA (Tutorships)
MOURIÑO MOSQUERA, ANTONIO (Co-tutorships)
PAZ CASTAÑAL, MANUEL MARIA (Tutorships)
MOURIÑO MOSQUERA, ANTONIO (Co-tutorships)
Court
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)
TORNEIRO ABUIN, MERCEDES (Chairman)
Fraile Carrasco, Alberto (Secretary)
Filippone , Salvatore (Member)