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991.
992.
Methylation of the enantiopure functionalized vinyl sulfoximines 5a-e and 14a-d followed by a F- ion or DBU-mediated isomerization of the vinyl aminosulfoxonium salts 7a-e and 15a-d, respectively, gave the allyl aminosulfoxonium salts 10a-e and 17a-d, respectively. A concomitant intramolecular substitution of the aminosulfoxonium group of 10a-e and 17a-d by the amino group afforded the unsaturated prolines 8a-e and 18a-d, respectively. The starting vinyl sulfoximines are accessible through a highly selective and stereo-complementary aminoalkylation of the corresponding sulfonimidoyl-substituted mono- and bis(allyl)titanium complexes with the imino ester 4. The vinyl aminosulfoxonium salts 34, 7a-d, and E-15c experienced upon treatment with the Cl- ion a migratory substitution with formation of the delta-chloro-beta,gamma-dehydro amino acids 36, E/Z-37a-d, and 38, respectively. A migratory substitution of the hydroxy-substituted vinyl aminosulfoxonium salts 46a and 46b furnished the delta-chloro allyl alcohols E/Z-48a and E-48b, respectively. A facile one-pot conversion of the vinyl sulfoximines 31b, 5c and 45a to the allyl chlorides 36, E/Z-37c and E/Z-48a, respectively, was achieved upon treatment with a chloroformiate. A tandem cyclization of the vinyl aminosulfoxonium salts 7b, Al-7b and 57 with LiN(H)tBu yielded the cyclopentanoid keto aminosulfoxonium ylides 54, Al-54, 59, 60 and 61, respectively. The structure of the tricyclic keto aminosulfoxonium ylide Al-54 has been determined by X-ray crystal structure analysis. Ab initio calculations and a NBO analysis of the tricyclic keto aminosulfoxonium ylide XXIII show a polar structure stabilized by electrostatic interactions between the ylidic C atom and both the carbonyl C atom and the S atom.  相似文献   
993.
Reddy BV  Reddy LR  Corey EJ 《Organic letters》2006,8(15):3391-3394
[Structure: see text] Under special conditions, N-phthaloyl-alpha-amino acid amides of 8-aminoquinoline can be either acetoxylated or arylated selectively at the beta-carbon. In certain cases, arylation can be effected at the gamma-carbon.  相似文献   
994.
The first total synthesis of (R)-gamma-indomycinone has been achieved which allowed the determination of the configuration of the stereogenic center of natural gamma-indomycinone as (S). The approach stands out for its generality and efficiency. [reaction: see text]  相似文献   
995.
While LC finds enormously widespread use in almost all areas of chemical science, the technique is limited as a means of identification because compounds do not elute with unique retention times. This limitation spurred the growth of hyphenated instrumental methods of analysis, such as LC-MS/MS, which because of the MS/ MS detection became a method of identification. However, techniques like LC-MS/ MS are specialised and require high initial purchase and running costs, inhibiting the more widespread growth of the technique. In an attempt to increase the separation power of LC, multi-dimensional LC was developed. This expanded the separation space and subsequently has allowed the development of methods with fingerprinting ability due to the lower probability of component overlap. The work in this study illustrates the application of 2-D LC as a means of chemical fingerprinting. We employed a sample base of various low molecular weight oligostyrenes and their diastereomers that represent a population of compounds whose selectivities in a one-dimensional separation are almost unity and hence essentially impossible to separate. Yet in a 2-D domain almost all individual components occupy unique 2-D retention times.  相似文献   
996.
Reddy LR  Reddy BV  Corey EJ 《Organic letters》2006,8(13):2819-2821
[reaction: see text] A useful process for the position-selective remote bromination of N-trifluoroacetyl-alpha-amino esters is illustrated for the isoleucine case. The 5-bromoisoleucine derivative shown above can be used for the synthesis of many modified amino acids, as described herein.  相似文献   
997.
In this paper, a new mathematical framework based on h, p, k and variational consistency (VC) of the integral forms is utilized to develop a finite element computational process of two‐dimensional polymer flows utilizing Oldroyd‐B constitutive model. Alternate forms of the choices of dependent variables in the governing differential equations (GDEs) are considered and is concluded that u, v, p, τ choice yielding strong form of the GDEs is meritorious over others. It is shown that: (a) since, the differential operator in the GDEs is non‐linear, Galerkin method and Galerkin method with weak form are variationally inconsistent (VIC). The coefficient matrices in these processes are non‐symmetric and hence may have partial or completely complex basis and thus the resulting computational processes may be spurious. (b) Since the VC of the VIC integral forms cannot be restored through any mathematically justifiable means, the computational processes in these approaches always have possibility of spurious solutions. (c) Least squares process utilizing GDEs in u, v, p, τ (strong form of the GDEs) variables (as well as others) is variationally consistent. The coefficient matrices are always symmetric and positive definite and hence always have a real basis and thus naturally yield computational processes that are free of spurious solutions. (d) The theoretical solution of the GDEs are generally of higher order global differentiability. Numerical simulations of such solutions in which higher order global differentiability characteristics of the theoretical solution are preserved, undoubtedly requires local approximations in higher order scalar product spaces . (e) LSP with local approximations in spaces provide an incomparable mathematical and computational framework in which it is possible to preserve desired characteristics of the theoretical solution in the computational process. Numerical studies are presented for fully developed flow between parallel plates and a lid driven square cavity. M1 fluid is used in all numerical studies. The range of applicability of the Oldroyd‐B model or lack of it is examined for both model problems for increasing De. A mathematical idealization of the corners where stationary wall meets the lid is presented and is shown to simulate the real physics when the local approximations are in higher order spaces and when hd→0. For both model problems shear rate is examined in the flow domain to establish validity of the Oldroyd‐B constitutive model. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   
998.
We reexamine the surface composition of strange stars. Strange quark stars are hypothetical compact stars which could exist if strange quark matter was absolutely stable. It is widely accepted that they are characterized by an enormous density gradient (10(26) g/cm4) and large electric fields at the surface. By investigating the possibility of realizing a heterogeneous crust, comprised of nuggets of strange quark matter embedded in an uniform electron background, we find that the strange star surface has a much reduced density gradient and negligible electric field. We comment on how our findings will impact various proposed observable signatures for strange stars.  相似文献   
999.
The bicyclic triaminophosphine P(RNCH(2)CH(2))(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.  相似文献   
1000.
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