2305-05-7Relevant articles and documents
Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes
Miura, Tomoya,Oku, Naoki,Murakami, Masahiro
, p. 14620 - 14624 (2019)
We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.
Total synthesis of insect pheromones (R)-4-dodecanolide and (S)-5-hexadecanolide
Sabitha, Gowravaram,Reddy, E. Venkata,Yadagiri,Yadav
, p. 3270 - 3274 (2006)
The asymmetric total synthesis of naturally occurring insect pheromones, (R)-4-dodecanolide and (S)-5-hexadecanolide has been achieved in a simple and efficient way with high yields. Georg Thieme Verlag Stuttgart.
Highly enantioselective reduction of alkynyl ketones by a binaphthol-modified aluminium hydride reagent. Asymmetric synthesis of some insect pheromones
Nishizawa,Yamada,Noyori
, p. 247 - 250 (1981)
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Synthesis of both the enantiomers of 4-dodecanolide, the pheromone of the rove beetle
Chattopadhyay,Mamdapur,Chadha
, p. 3667 - 3672 (1990)
A simple and efficient synthesis of the target pheromone in its enantiomeric forms has been formulated using easily accessible (R)-2,3- isopropanedioxyglyceraldehyde (2) as the single starting chiron.
Stereoselective synthesis of chiral δ-lactonesviaan engineered carbonyl reductase
Wang, Tao,Zhang, Xiao-Yan,Zheng, Yu-Cong,Bai, Yun-Peng
, p. 10584 - 10587 (2021/10/19)
A carbonyl reductase variant,SmCRM5, fromSerratia marcescenswas obtained through structure-guided directed evolution. The variant showed improved specific activity (U mg?1) towards most of the 16 tested substrates and gave high stereoselectivities of up to 99% in the asymmetric synthesis of 13 γ-/δ-lactones. In particular, SmCRM5showed a 13.8-fold higher specific activity towards the model substrate,i.e., 5-oxodecanoic acid, and gave (R)-δ-decalactone in 99% ee with a space-time yield (STY) of 301 g L?1d?1. The preparative synthesis of six δ-lactones in high yields and with high enantiopurities showed the feasibility of the biocatalytic synthesis of these high-value-added chemicals, providing a cost-effective and green alternative to noble-metal catalysis.
CYP505E3: A Novel Self-Sufficient ω-7 In-Chain Hydroxylase
Maseme, Mpeyake Jacob,Opperman, Diederik Johannes,Pennec, Alizé,Smit, Martha Sophia,van Marwijk, Jacqueline
supporting information, p. 10359 - 10362 (2020/04/23)
The self-sufficient cytochrome P450 monooxygenase CYP505E3 from Aspergillus terreus catalyzes the regioselective in-chain hydroxylation of alkanes, fatty alcohols, and fatty acids at the ω-7 position. It is the first reported P450 to give regioselective in-chain ω-7 hydroxylation of C10–C16 n-alkanes, thereby enabling the one step biocatalytic synthesis of rare alcohols such as 5-dodecanol and 7-tetradecanol. It shows more than 70 percent regioselectivity for the eighth carbon from one methyl terminus, and displays remarkably high activity towards decane (TTN≈8000) and dodecane (TTN≈2000). CYP505E3 can be used to synthesize the high-value flavour compound δ-dodecalactone via two routes: 1) conversion of dodecanoic acid into 5-hydroxydodecanoic acid (24 percent regioselectivity), which at low pH lactonises to δ-dodecalactone, and 2) conversion of 1-dodecanol into 1,5-dodecanediol (55 percent regioselectivity), which can be converted into δ-dodecalactone by horse liver alcohol dehydrogenase.
Efficient Stereoselective Synthesis of Structurally Diverse γ- and δ-Lactones Using an Engineered Carbonyl Reductase
Chen, Meng,Zhang, Xiao-Yan,Xing, Chen-Guang,Zhang, Chao,Zheng, Yu-Cong,Pan, Jiang,Xu, Jian-He,Bai, Yun-Peng
, p. 2600 - 2606 (2019/05/21)
Structurally diverse γ- and δ-lactones were efficiently synthesized stereoselectively using an engineered carbonyl reductase from Serratia marcescens (SmCRV4). SmCRV4 exhibited improved activity (up to 500-fold) and thermostability toward 14 γ-/δ-keto acids and esters, compared with the wild-type enzyme, with 110-fold enhancement in catalytic efficiency (kcat/Km) toward methyl 4-oxodecanoate. The preparative synthesis of alkyl and aromatic γ- and δ-lactones with 95 %–>99 % ee and 78 %–90 % yields was demonstrated. The highest space-time yield, 1175 g L?1 d?1, was achieved for (R)-γ-decalactone.
