On forced coastal trapped waves at low latitudes in a stratified ocean

The response on the continental shelf and slope of a baroclinic ocean to driving by an alongshore wind stress at the coast

Central equatorial Pacific zonal currents. I: The Sverdrup balance, nonlinearity and tropical instability waves. Annual mean dynamics

Several recent observational studies of central Pacific equatorial current dynamics have suggested that, in the vertical integral between the surface and the thermocline, the linear equatorial Sverdrup balance holds. However, in a high vertical resolution ocean general circulation model, we find that nonlinearity is an order (1) element of the local and the vertically integrated balances on and near the equator at 140W. Although this OGCM has been used in many studies of the tropical Pacific, its equatorial zonal momentum equation balances have never been described in detail and compared with observations. We describe the annual mean balances here, identify the similarities and differences between the model balances and observational estimates of the balances, and discuss various reasons why the model and the observations may disagree in the respects that they are found to do so. The term balances vary strongly with latitude and depth; the system is nonlinear and three dimensional. There is little tendency for pairs of terms (e.g., the meridional and vertical advection terms) to balance locally or in the vertical integral. Every term in the zonal momentum equation plays a role somewhere in the analysis region discussed here. Thus the generality of point estimates of these balances is small. The Tropical Instability Wave zonal momentum flux divergence, although not an O (1) term in the balance, acts like a \u27negative viscosity\u27 over the upper 40 m on the equator; its tendency is to drive westward flow. If the ocean balances resemble those of the model dynamics, gaining detailed perspective on the zonal balances will require a major observational effort. Because there is strong subseasonal and interannual variability of the flows in the central equatorial Pacific, time-mean balances are not simple to estimate. Further, special attention will have to be given to resolving the shears in the upper 50 m, because it is over these depths that the model and observational results differ most strongly. We suggest that the widely used technique of extrapolating the near-surface currents based on their shears in the uppermost bins of the ADCP profiles deserves careful scrutiny; subsampling the model flow profiles in this fashion leads to important errors. Until the strong vertically sheared very near-surface current field is observed accurately it will not be possible to determine if the model results are correct, but we suggest that the existing observational results should not be regarded as definitive

Central equatorial Pacific zonal currents. II: The seasonal cycle and the boreal spring surface eastward surge

The seasonally averaged zonal momentum equation tendencies at 140W are studied in a high-resolution primitive equation ocean general circulation model simulation of the tropical Pacific. The model experiment, forced by climatological monthly average wind-stress, reproduces well the observed boreal springtime eastward surge of the normally westward surface flow, as well as many features of the acceleration and deceleration between the surface and 200 m between January and October. We present each of the zonal momentum equation tendency terms for the depth range 0-160 m, but our discussion focuses on the behavior of the boreal springtime near-surface flow, perhaps the most distinctive feature of the seasonal cycle. The eastward surface surge in boreal spring depends crucially on the springtime weakening of the otherwise westward tendency from tropical instability waves (TIWs). The TIW effects, together with the eastward tendency from the seasonal weakening of the easterly wind-stress, drive the eastward surface current surge. Although the \u27negative viscosity\u27 effect of the TIWs is small in the annual mean, as we have previously shown, its seasonal variation is necessary to the surface flow reversal and eastward surge in this model. A series of experiments, each with weaker TIWs than its predecessor, shows a progressive weakening and eventual absence of springtime eastward surface flow, supporting the above analysis. The seasonal zonal velocity accelerations and decelerations are small compared with the terms in the zonal momentum equation; these terms must be known to an accuracy of at least 10 cm s-1 month-1 (2-5% of the largest terms) if a meaningful budget is to be obtained. This is a strong constraint that must be planned for in future observational studies. We find that nonlinear terms are O (1) in the vertically-integrated balance as well as the local balance, in contrast with some recent observational estimates. Extrapolated velocity errors, neglected terms, data processing assumptions, and crude finite-differencing in the observational studies may account for the differences, as appeared to be the case in the annual mean balances. The model dynamical balances cannot be reproduced if the methods used to analyze observational data are applied to the model output fields. Very near-surface currents must be measured rather than extrapolated if the ocean shear is similar to that of the model flows

Synthesis and acylation of 1,3-thiazinane-2-thione

1. Procedure (Note 1) A. 3-Ammoniopropylsulfate (1). An oven-dried single-necked 100 mL round-bottomed flask (14/23 joint), equipped with a 2.5-cm Teflon-coated magnetic stirbar, is charged with 3-amino-1-propanol (11.5 mL, 150 mmol, 1 equiv) (Note 2) and anhydrous dichloromethane (35 mL) (Note 3). A 50 mL pressure-equalizing addition funnel (14/23 joint) equipped with a CaCl2 tube is attached to the round-bottomed flask and is then charged with chlorosulfonic acid (10.5 mL, 159 mmol, 1.06 equiv) (Note 4) using a 20 mL glass luer-lock syringe. The flask is immersed in an ice/water bath and the solution is stirred for 5 min. The chlorosulfonic acid is added dropwise over 30 min, allowing the fumes to escape. A white precipitate is formed during the addition. Once the addition is complete, the reaction is stirred at 0 °C for 20 min and left to warm slowly to room temperature over 30 min (Note 5). Once at room temperature, the reaction mixture is stirred for 1 h. The resulting mixture is filtered through a 70 mm diameter Number 3 Glass filter funnel with a Büchner setup. A bent spatula and methanol (25 mL) (Note 6) are used to remove remaining product from the flask walls. The mixture in the filter funnel is triturated with methanol (40 mL, then 2 × 20 mL) (Note 6), using a spatula to break up the lumps each time. The resulting white solid is broken up into a coarse powder and transferred to a 100 mL round-bottomed flask (29/32 joint), where it is placed on a rotary evaporator (40 °C, 12 mmHg pressure) for 1 h. The resulting white solid is ground to a fine white powder using a 10 cm diameterglass mortar and pestle, retransferred to a 100 mL round-bottomedflask and dried on a high vacuum line (25 °C, 0.1 mmHg pressure) for 2 h giving the title compound 1 (20.72 g, 134 mmol, 89% yield) (Note 7) as a fine white powder

Diastereoselective and catalytic α-alkylation of chiral N-acyl thiazolidinethiones with stable carbocationic salts

Direct nickel-catalyzed alkylation of chiral N-acyl-4-isopropyl-1,3-thiazolidine-2-thiones using a commercially available nickel(II) complex, (Me3P)2NiCl2, has been developed for tropylium and trityl tetrafluoroborate salts. The reaction provides a single diastereomer of the corresponding adducts in good to high yields, which, in turn, can be easily converted into a wide array of enantiomerically pure compounds that are difficult to obtain by other asymmetric procedures

General and stereoselective aminoxylation of biradical titanium(IV) enolates with TEMPO: a detailed study on the effect of the chiral auxiliary

A comprehensive analysis of the influence of the chiral auxiliary on the α-aminoxylation of titanium(IV) enolates with TEMPO indicated that (S) 4-tert-butyl-1-oxazolidine-2-thione is the most appropriate scaffold to provide a single diastereomer in high yields for a variety of substrates, which converts such a radical reaction into a highly chemo- and stereoselective oxidatio

Direct and Asymmetric Aldol Reactions of N-Azidoacetyl-1,3-thiazolidine-2-thione Catalyzed by Chiral Nickel(II) Complexes. A New Approach to the Synthesis of -Hydroxy--Amino Acids

A direct and asymmetric triisopropylsilyltrifluoromethanesulfonate (TIPSOTf) mediated aldol reaction of N-azidoacetyl-1,3-thiazolidine-2-thione with aromatic aldehydes catalyzed by a chiral nickel(II)-Tol-BINAP complex has been developed (BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). The catalytic protocol gives the corresponding anti α-azido-β-silyloxy adducts with outstanding stereocontrol and in high yields. Theoretical calculations account for the stereochemical outcome of the reaction and lay the foundations for a mechanistic model. In turn, the easy removal of the thiazolidinethione yields a wide array of enantiomerically pure derivatives in a straightforward and efficient manner. Such a noteworthy character of the heterocyclic scaffold together with the appropriate manipulation of the azido group open a new route to the synthesis of di- and tripeptide blocks containing a β-aryl-β-hydroxy-α-amino acid

Direct and asymmetric nickel(II)-catalyzed construction of carbon−carbon bonds from N‑acyl thiazinanethiones

A wide array of new N-acyl thiazinanethiones are employed in a number of direct and enantioselective carbon-carbon bond forming reactions catalyzed by nickel(II) complexes. The electrophilic species are mostly prepared in situ from ortho esters, methyl ethers, acetals, and ketals, which makes the overall process highly efficient and experimentally straightforward. Theoretical calculations indicate that the reactions pro-ceed through an open transition state in a SN1-like mechanism. The utility of this novel procedure has been demonstrated by the asymmetric preparation of syntheti-cally useful intermediates and the total synthesis of pe-peromin D

Direct and enantioselective aldol reactions catalyzed by chiral nickel(II) complexes

A direct and asymmetric aldol reaction of N-acylthiazinanethiones with aromatic aldehydes catalyzed by chiralnickel(II) complexes is reported. The reaction gives thecorresponding O-TIPS-protected anti-aldol adducts in highyields and with remarkable stereocontrol and atom economy.Furthermore, the straightforward removal of the achiralscaffold provides enantiomerically pure intermediates ofsynthetic interest, which involve precursors for anti-a-amino-b-hydroxy anda,b-dihydroxy carboxylic derivatives. Theoret-ical calculations explain the observed high stereocontrol

Direct, stereodivergent, and catalytic Michael additions of thioimides to α,β-unsaturated aldehydes – Total synthesis of Tapentadol

Direct and stereodivergent Michael additions of N-acyl 1,3-thiazinane-2-thiones to α,β-unsaturated aldehydes catalyzed by chiral nickel(II) complexes are reported. The reactions proceed with a remarkable regio-, diastereo-, and enantioselectivity, so access to any of the four potential Michael stereoisomers is granted through the appropriate choice of the chiral ligand of the nickel(II) complex. Simple removal of the heterocyclic scaffold furnishes a wide array of either syn or anti enantiomerically pure derivatives, which can be exploited for the asymmetric synthesis of biologically active compounds, as demonstrated in a new approach to tapentadol. In turn, a mechanism, based on theoretical calculations, is proposed to account for the stereochemical outcome of these transformations