01458nas a2200217 4500008004100000022001400041245013200055210006900187260007500256300001400331490000600345520063000351653001200981653002000993653002101013653001801034653001201052100002201064700002401086856013001110 2015 eng d a1867-388000aHighly regioselective isomerizing hydroformylation of long-chain internal olefins catalyzed by a rhodium bis(phosphite) complex0 aHighly regioselective isomerizing hydroformylation of longchain  aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcNOV a3468-34710 v73 a

The single-step synthesis, coordination behavior, and application of a bis(phosphite) ligand in the isomerizing hydroformylation of internal olefins was investigated. Interestingly, high-pressure NMR spectroscopy investigations revealed unexpected inequivalency of the two phosphorus nuclei, which display bisequatorial coordination of the bis(phosphite) ligand in a trigonal bipyramidal rhodium complex. Upon employment in the isomerizing hydroformylation of the exceedingly challenging plant oil derived substrate methyl oleate, the bis(phosphite) rhodium complex revealed an unprecedented linear selectivity of 75%.

10aalkenes10abis(phosphite)s10aHydroformylation10aisomerization10aRhodium1 aPandey, Swechchha1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/highly-regioselective-isomerizing-hydroformylation-long-chain-internal-olefins-catalyzed-001629nas a2200157 4500008004100000245006000041210006000101260000800161300001400169490000600183520112100189100002201310700002301332700002401355856009201379 2017 eng d00aIsomerizing hydroformylation of cashew nut shell liquid0 aIsomerizing hydroformylation of cashew nut shell liquid cOCT a3997-40040 v93 aA small library of bisphosphorus ligands was evaluated in the rhodium-catalyzed isomerizing hydroformylation (I-HF) of cashew nut shell liquid (CNSL). The rhodium complex of 1,2-bis((di-tert-butylphosphanyl)methyl)benzene (BDTBPMB; L4) outperformed the other bisphosphite and bisphosphine ligands and unveiled a moderate selectivity of 28% and 50% in the I-HF of CNSL monoene and methoxy-protected monoene, respectively. The resultant aldehyde 16-(3-methoxyphenyl)hexadecanal P1 was isolated and its identity was fully established. Application of bis-phosphine ligand L4 in the I-HF of highly challenging CNSL cardanol (S3) and methoxy-protected CNSL cardanol yielded a linear selectivity of 74%, although with reduced conversion. To demonstrate the synthetic utility of our strategy, the obtained aldehyde (derived from S3) was subjected to hydrogenation and the resultant 3-(16-hydroxyhexadecyl) phenol (P8) was isolated in 89% isolated yield. High-pressure NMR investigation revealed selective formation of a bis-equatorial BDTBPMB-rhodium complex, which might be responsible for the excellent linear selectivity.1 aPandey, Swechchha1 aShinde, Dinesh, R.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/isomerizing-hydroformylation-cashew-nut-shell-liquid02077nas a2200181 4500008004100000245010200041210006900143260000800212300001400220490000800234520140600242100002401648700002501672700002201697700002101719700002401740856013101764 2017 eng d00aSynthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation0 aSynthesis of metasubstituted monodentate phosphinite ligands and cAUG a1143-11520 v1293 aSynthesis of meta-substituted phosphinite ligands 3,3'-(methoxyphosphanediyl) bis(N, N-diethylaniline) (4a) and methoxybis(3-methoxyphenyl) phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110-120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas 4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions. Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functional olefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85-90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33-42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).1 aDeshmukh, Satej, S.1 aGaikwad, Shahaji, R.1 aPandey, Swechchha1 aMali, Pramod, S.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/synthesis-meta-substituted-monodentate-phosphinite-ligands-and-implication-hydroformylation01217nas a2200205 4500008004100000022001400041245007900055210006900134260000800203300001400211490000700225520052200232100002700754700002200781700002400803700002100827700002300848700003000871856011000901 2018 eng d a1359-734500aImido-P(V) trianion supported enantiopure neutral tetrahedral Pd(II) cages0 aImidoPV trianion supported enantiopure neutral tetrahedral PdII  cFEB a1873-18760 v543 a

Charge-neutral chiral hosts are attractive due to their ability to recognize a wide range of guest functionalities and support enantio-selective processes. However, reports on such charge-neutral cages are very scarce in the literature. Here, we report an enantiomeric pair of tetrahedral Pd(II) cages built from chiral tris(imido) phosphate trianions and oxalate linkers, which exhibit enantioselective separation capabilities for epichlorohydrin, beta-butyrolactone, and 3-methyl- and 3-ethyl cyclopentanone.

1 aRajasekar, Prabhakaran1 aPandey, Swechchha1 aPaithankar, Harshad1 aChugh, Jeetender1 aSteiner, Alexander1 aBoomishankar, Ramamoorthy uhttps://library.ncl.res.in/content/imido-pv-trianion-supported-enantiopure-neutral-tetrahedral-pdii-cages02690nas a2200229 4500008004100000022001400041245011000055210006900165260000900234300001400243490000800257520190300265100002202168700001502190700002302205700001702228700002402245700002402269700001802293700002402311856012502335 2018 eng d a0002-786300aIron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process0 aIron Catalyzed Hydroformylation of Alkenes under Mild Conditions cMAR  a4430-44390 v1403 a

Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 degrees C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)(4)](-)[Ph3PNPPh3](+) (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)(2)(PPh3)(2)] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.

1 aPandey, Swechchha1 aRaj, Vipin1 aShinde, Dinesh, R.1 aVanka, Kumar1 aKashyap, Varchaswal1 aKurungot, Sreekumar1 aVinod, C., P.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/iron-catalyzed-hydroformylation-alkenes-under-mild-conditions-evidence-feii-catalyzed01510nas a2200205 4500008004100000022001400041245009900055210006900154260000800223300001600231490000700247520077700254100002701031700002201058700002401080700002001104700002401124700003001148856012601178 2019 eng d a0020-166900aChiral separation of styrene oxides supported by enantiomeric tetrahedral neutral Pd(II) cages0 aChiral separation of styrene oxides supported by enantiomeric te cNOV a15017-150200 v583 a

The separation of enantiomers is of considerable importance in the preparation of the compounds of biological interests, catalysis, and drug development. Here, we report a novel enantioseparation of styrene epoxides (SOs) resolved in the presence of a pair of enantio-enriched tetrahedral cages. Chiral neutral cages of formula [(Pd3X*)(4)(C6O4Cl2)(6)] ([X*](3-) = RRR-or SSS-[PO(N(*CH(CH3)Ph)(3)](3)) are constructed from Pcl, building units supported by tris(imido)phosphate trianions and chloranilate linkers. These cages exhibit considerable enantioselective separation capabilities toward a series of styrene epoxides via a crystallization inclusion method. A highest enantiomeric excess (ee) value of up to 80% is achieved for the (R)-4-fluorostyrene oxide.

1 aRajasekar, Prabhakaran1 aPandey, Swechchha1 aFerrara, Joseph, D.1 aDel Campo, Mark1 aLe Magueres, Pierre1 aBoomishankar, Ramamoorthy uhttps://library.ncl.res.in/content/chiral-separation-styrene-oxides-supported-enantiomeric-tetrahedral-neutral-pdii-cages01736nas a2200169 4500008004100000022001400041245008100055210006900136260000800205300001400213490000700227520114900234100002201383700002601405700002401431856011101455 2021 eng d a1463-926200aRefining plant oils and sugars to platform chemicals, monomers, and polymers0 aRefining plant oils and sugars to platform chemicals monomers an cMAY a4255-42950 v233 a

As fossil resources continue to dwindle and environmental concerns are magnified, finding sustainable alternatives is the only way to mitigate resource availability and derisk the planet. The principles of Green Chemistry may provide guidance in this case, and renewable resources can be converted into useful platform chemicals, monomers, and polymers. This critical review examines the possibility of utilizing renewable plant oils and sugars to produce feedstock chemicals, monomers, and polymers. Among the seven isomerizing functionalization reactions of plant oils, isomerizing alkoxycarbonylation displays the highest terminal selectivity. Despite the low reactivity of sugar-derived isohexides, new strategies have been deployed to convert isohexides into difunctional monomers and polymers. The commercialization of isohexides and a few polymers derived from these building blocks has just commenced. Thus, challenges associated with isomerizing functionalization of plant oils and the use of sugar-derived isohexides in chemical syntheses have been summarized, and the potential of these renewable resources has been evaluated.

1 aPandey, Swechchha1 aRajput, Bhausaheb, S.1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/refining-plant-oils-and-sugars-platform-chemicals-monomers-and-polymers02053nas a2200277 4500008004100000022001400041245011600055210006900171260000800240300001500248490000900263520112800272653002901400653001401429653001901443653002201462653003101484100001701515700001701532700002201549700001501571700001701586700001701603700002401620856013101644 2022 eng d a1434-193X00aMechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation0 aMechanistically guided one pot synthesis of phosphinephosphite a cJAN ae2021014470 v20223 a

Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.

10aasymmetric hydrogenation10acatalysis10aDOPA synthesis10aOne pot synthesis10aPhosphine-phosphite ligand1 aSen, Anirban1 aKumar, Rohit1 aPandey, Swechchha1 aRaj, Vipin1 aKumar, Pawan1 aVanka, Kumar1 aChikkali, Samir, H. uhttps://library.ncl.res.in/content/mechanistically-guided-one-pot-synthesis-phosphine-phosphite-and-its-implication-asymmetric